Methods for renewable fuels with reduced waste streams

ABSTRACT

The present application generally relates to the introduction of a reduced volatility renewable fuel oil as a feedstock and processing it with a petroleum stream in the presence of a catalyst to reduce the generation of waste streams in refinery systems or field upgrading equipment.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/709,822, filed Dec. 10, 2012, which application is fully incorporatedherein by reference in its entirety. This application also claimspriority to: U.S. Provisional Application No. 61/569,712, filed Dec. 12,2011; U.S. Provisional Application No. 61/646,152, filed May 11, 2012;and U.S. Provisional Application No. 61/673,683, filed Jul. 19, 2012.Priority to each of these provisional applications is expressly claimed,and the disclosures of each of these respective provisional applicationsare hereby incorporated by reference in their entireties for allpurposes.

The present disclosure relates to: U.S. Pat. No. 7,905,990; U.S. Pat.No. 5,961,786; and U.S. Pat. No. 5,792,340, each of which are herebyfurther incorporated by reference in their entirety.

FIELD OF THE INVENTION

The present disclosure generally relates to the introduction of arenewable fuel or renewable oil as a feedstock into refinery systems orfield upgrading equipment. More specifically, the present disclosure isdirected to methods of introducing a liquid thermally produced frombiomass into a petroleum conversion unit; for example, a refinery fluidcatalytic cracker (FCC), a coker, a field upgrader system, ahydrocracker, and/or hydrotreating unit; for co-processing withpetroleum fractions, petroleum fraction reactants, and/or petroleumfraction feedstocks and the products, e.g., fuels, and uses and value ofthe products resulting therefrom.

BACKGROUND

Biomass has been a primary source of energy over much of human history.During the late 1800's and 1900's the proportion of the world's energysourced from biomass dropped, as the commercial development andutilization of fossil fuels occurred, and markets for coal and petroleumproducts dominated. Nevertheless, some 15% of the world's energycontinues to be sourced from biomass, and in developing countries thecontribution of biomass is much higher at 38%. In addition, there hasbeen a new awareness of the impact of the utilization of fossil fuels onthe environment. In particular, the contribution of greenhouse gases, asa result of consuming fossil fuels.

Biomass, such as wood, wood residues, and agricultural residues, can beconverted to useful products, e.g., fuels or chemicals, by thermal orcatalytic conversion. An example of thermal conversion is pyrolysiswhere the biomass is converted to a liquid and char, along with agaseous co-product by the action of heat in essentially the absence ofoxygen.

In a generic sense, pyrolysis is the conversion of biomass to a liquidand/or char by the action of heat, typically without involving anysignificant level of direct combustion of the biomass feedstock in theprimary conversion unit.

Historically, pyrolysis was a relatively slow process where theresulting liquid product was a viscous tar and “pyroligneous” liquor.Conventional slow pyrolysis has typically taken place at temperaturesbelow 400° C., and over long processing times ranging from severalseconds to minutes or even hours with the primary intent to producemainly charcoal and producing liquids and gases as by-products.

A more modern form of pyrolysis, or rapid thermal conversion, wasdiscovered in the late 1970's when researchers noted that an extremelyhigh yield of a light, pourable liquid was possible from biomass. Infact, liquid yields approaching 80% of the weight of the input of awoody biomass material were possible if conversion was allowed to takeplace over a very short time period, typically less than 5 seconds.

The homogeneous liquid product from this rapid pyrolysis, which has theappearance of a light to medium petroleum fuel oil, can be consideredrenewable oil. Renewable oil is suitable as a fuel for clean, controlledcombustion in boilers, and for use in diesel and stationary turbines.This is in stark contrast to slow pyrolysis, which produces a thick, lowquality, two-phase tar-aqueous mixture in very low yields.

In practice, the short residence time pyrolysis of biomass causes themajor part of its organic material to be instantaneously transformedinto a vapor phase. This vapor phase contains both non-condensable gases(including methane, hydrogen, carbon monoxide, carbon dioxide andolefins) and condensable vapors. It is the condensable vapors thatconstitute the final liquid product, when condensed and recovered, andthe yield and value of this liquid is a strong function of the methodand efficiency of the downstream capture and recovery system.

Given the fact that there is a limited availability of hydrocarbon crudeand an ever increasing demand for energy, particularly liquidtransportation fuels, alternative sources are therefore required. Theabundance and sustainability of biomass makes this renewable feedstockan attractive option to supplement the future demand for petroleum. Thedifficulty with biomass is the fact that it contains oxygen, unlikeconventional hydrocarbon fuels, and historically has not been readilyconvertible into a form that can be easily integrated into existinghydrocarbon based infrastructure.

A significant amount of work has been done to investigate the productionof liquid hydrocarbon fuels from biomass by various thermal andthermocatalytic schemes. U.S. Pat. No. 5,792,340; U.S. Pat. No.5,961,786; Lappas et al., Biomass Pyrolysis in a Circulating Fluid BedReactor for the Production of Fuels and Chemicals, Fuel 81 (2002),2087-2095); and Samolada et al., Catalyst Evaluation for CatalyticBiomass Pyroloysis, Fuel & Energy 2000, 14, 1161-1167, describe thedirect processing of biomass or other oxygenated carbonaceous feedstocksin a circulating fluid bed reactor using a catalyst (zeolite FCCcatalyst) as the solid circulating media in an effort to directlydeoxygenate the biomass and produce transportation fuels or fuel blends,as well as other hydrocarbons. Although some hydrocarbon products wereproduced, the yields were unacceptably low, and there was a high yieldof char or coke and by-product gas produced. In addition, there werefrequent issues with reactor fouling and plugging, and other serioustechnical difficulties associated with catalyst performance. Not onlywere the liquid yields lower, much of liquid product produced wouldrequire further upgrading and treatment to enable any direct immediateuse in place of fossil fuel-based hydrocarbons.

Given the above limitations, another alternative for hydrocarbonproduction from biomass is to convert solid biomass first into athermally-produced or thermocatalytically-produced liquid, and then feedthis neat liquid (i.e. 100% liquid biomass product) into a circulatingfluid bed reactor using a FCC catalyst or other appropriate catalyst asthe solid circulating media (Adjaye et al., Production of Hydrocarbonsby Catalytic Upgrading of a Fast Pyrolysis Bio-oil, Fuel ProcessingTechnology 45 (1995), 185-192). Again, in this case, unacceptablehydrocarbon yields were achieved, reactor plugging and fouling was oftenevident, and much of the feedstock was converted to char/coke, gas andan oxygen-rich liquid that tended to separate into different liquidphases.

The use of catalytic cracking of a solid or liquid biomass, abiomass-derived vapor, or a thermally-produced liquid as a means toproduce hydrocarbons from oxygenated biomass is technically complex,relatively inefficient, and produces significant amounts of low valuebyproducts. To solve the catalyst and yield issues, researchers lookedat stand-alone upgrading pathways where biomass-derived liquids could beconverted to liquid hydrocarbons using hydrogen addition and catalystsystems in conversion systems that were tailored specifically for theprocessing of oxygenated materials (Elliott, Historical Developments inHydroprocessing Bio-oils, Energy & Fuels 2007, 21, 1792-1815). Althoughtechnically feasible, the large economies-of-scale and the technicalcomplexities and costs associated with high-pressure multi-stagehydrogen addition (required for complete conversion to liquidhydrocarbon fuels) are severely limiting and generally viewed asunacceptable.

As a means to overcome the technical and economic limitations associatedwith full stand-alone biomass upgrading to transportation fuels,researchers (de Miguel Mercader, Pyrolysis Oil Upgrading forCo-Processing in Standard Refinery Units, Ph.D Thesis, University ofTwente, 2010 (“Mercader”); Fogassy et al., Biomass Derived FeedstockCo-Processing with EGO for Hybrid Fule Production in FCC Units, Institutde Recherches sur la Catalyse et l'Environnement de Lyon, UMR5236CNRS-UCBL (“Fogassy”); Gutierrez et al., Co-Processing of UpgradedBio-Liquids in Standard Refinery Units—Fundamentals, 15^(th) EuropeanBiomass Conference & Exhibition, Berlin May 7-11, 2007) are looking atvarious schemes for partial upgrading of the oxygenated biomass toreduce oxygen, followed by the co-processing of this intermediatebiomass product with petroleum feedstocks in existing petroleum refineryoperations. These initiatives are all focused on hydrodeoxygenation ofthe biomass-derived liquid prior to co-processing with petroleum, andare predicated on the consideration that hydrotreatment of the thermallyproduced liquid is necessary prior to petroleum co-processing in orderto avoid rapid FCC catalyst deactivation and reactor fouling, and topreclude excessive coke and gas production. Hence, the published studiesand prior art include the co-processing of petroleum in fluid catalyticcracking (FCC) refinery units with upgraded liquids that have beenhydrotreated after their initial thermal production from biomass.

The early FCC units traditionally used dense phase bed reactor systemsto enable good contact between the catalyst and the hydrocarbonfeedstock. Long residence times were required to ensure sufficientconversion of the feedstock to the desired product. As catalyst systemsimproved and the catalyst became more active, the FCC was redesigned toincorporate a riser configuration. The riser configuration enabledcontact times between the catalyst and hydrocarbon feedstock to bereduced to somewhere around 2 to 3 seconds (does not include anyresidence time in the reactor vessel or termination section).

One drawback of many, if not most of the early FCC designs was the risertermination systems that essentially linked the riser to an open reactorvessel that housed the solids separation devices. It had been recognizedfor several years that significant post riser thermal cracking occurs incommercial FCC units resulting in the substantial production of dry gasand other lower value products. The two mechanisms by which this occursare through thermal and dilute catalytic cracking. Thermal crackingresults from extended residence times of hydrocarbon vapors in thereactor disengaging area, and leads to high dry gas yields vianon-selective free radical cracking mechanisms. Dilute phase catalyticcracking results from extended contact between catalyst and hydrocarbonvapors downstream of the riser. While much of this was eliminated in thetransition from bed to riser cracking, there is still a substantialamount that can occur in the dilute phase due to significant catalystholdup which occurs without an advanced termination system design.

Many FCC vendors and licensors offer advanced riser termination systemsto minimize post-riser cracking, and many if not most units haveimplemented these in both new unit and revamp applications. In addition,some refiners have implemented their own “in-house” designs for the samepurpose. Given the complexity and diversity of FCC units as well as newunit design differences, there are many variations of these advancedtermination systems such as “closed” cyclones, “close-coupled” cyclones,“direct coupled” cyclones, “high containment systems”, “vortexseparation system”, etc. There are differences in the specific designs,and some may be more appropriate for specific unit configurations thanothers, but all serve the same fundamental purpose of reducing theundesirable post-riser reactions.

Contact time of the catalyst with the feedstock is comprised of theresidence time in the riser and often includes the residence time in theadvanced riser termination system as described above. Typical riserresidence times are about 2 to 3 seconds and the additional terminationsystem residence time may be about 1 to 2 seconds. This leads to anoverall catalyst contact time of about 3 to 5 seconds.

One innovative embodiment that forms part of the present application maybe to processes employing thermally-produced liquids in conjunction withpetroleum based materials in FCCs or field upgrader operations. Forexample, a method that includes the co-processing of an non-hydrotreatedbiomass derived liquid in small amounts with VGO or other crude oilbased liquids in the FCC or field upgrader operations.

Another innovative embodiment that forms part of the present applicationmay be for biomass conversion that the prior art has overlooked andintentionally avoided: the co-processing of non-upgraded,thermally-produced liquid with hydrocarbons in a manner which removesthe complexity of intermediate upgrading steps and yet may be stillcompatible with crude oil feedstock processing. As already indicated,the prior art has clearly shown that non-treated, thermally-producedbiomass liquids are not suitable for conversion to liquid hydrocarbonsdirectly in FCC and other catalytic conversion systems. Therefore whenvarious schemes of co-processing with petroleum in existing refineryoperations are considered in the prior art, including FCC co-processing,the co-processing of non-upgraded, non-treated thermal biomass liquidsmay be excluded from these co-processing options (Mercader; Fogassy).However, as set forth in the present disclosure, unexpected technicaland economic benefits are in fact evident in the co-processing ofthermally-derived biomass products with petroleum feedstocks in variousrefinery operations.

BRIEF SUMMARY OF THE APPLICATION

In certain embodiments, the invention relates a fuel composition derivedfrom a petroleum fraction feedstock and a renewable fuel oil feedstock.In certain embodiments, the invention relates a fuel composition derivedfrom a petroleum fraction feedstock and a renewable fuel oil feedstockco-processed in the presence of a catalyst. In certain embodiments, theinvention relates a fluidized catalytic cracker product compositionderived from a feedstock comprising a renewable fuel oil. In certainembodiments, the invention relates a fuel composition derived fromgreater than 80 wt. % of a petroleum fraction feedstock and less than 20wt. % of a renewable fuel oil feedstock that may have been processed inconversion unit, in the presence of a catalyst.

In certain embodiments, the invention relates to a fuel comprising aproduct of a conversion unit, such as a fluidized catalytic cracker,having a petroleum fraction and a renewable fuel oil as reactants. Incertain embodiments the invention relates to fuel comprising a productof a refinery conversion unit co-processing a petroleum fraction jointlywith a renewable fuel oil. In certain embodiments, the invention relatesto a fuel comprising a product of a refinery conversion unit wherein theconversion unit receives a petroleum fraction and a renewable fuel oil.

In certain embodiments, the invention relates to a method of preparing afuel, for example a transportation fuel, comprising providing arenewable fuel oil feedstock with a petroleum fraction feedstock in thepresence of a catalyst. In certain embodiments, the invention relates toa method of preparing a fuel, comprising processing a petroleum fractionfeedstock with a renewable fuel oil feedstock in the presence of acatalyst.

In certain embodiments, the invention relates to a method of preparing afuel comprising processing a petroleum fraction feedstock with arenewable fuel oil feedstock in the presence of a catalyst and,optionally, adjusting feed addition rates of the petroleum fractionfeedstock, the renewable fuel oil feedstock, or both, to target aparticular fuel product profile, riser temperature, or reaction zonetemperature; and/or, optionally, adjusting catalyst to combinedpetroleum fraction feedstock and renewable fuel oil feedstock ratio(catalyst:oil ratio) to target a particular fuel product profile, risertemperature, or reaction zone temperature; wherein the catalyst:oilratio is a weight ratio or a volume ratio.

In certain embodiments, the invention relates to a method ofco-processing a petroleum fraction feedstock and a renewable fuel oilsuch that the fuel product has at least 70 vol. % of gasoline and LCO orat least 70 vol. % of transportation fuel, relative to the total volumeof product resulting from the product stream of the conversion unit.

In certain embodiments, the invention relates to a method of improvingpetroleum conversion in a refinery, comprising processing a petroleumfraction substituted with a renewable fuel oil (on an equivalent energybasis and/or carbon content basis) in the presence of a catalyst.

In certain embodiments, the invention relates to a method of increasingfuel yield, for example the yield of one or more of gasoline, dieselfuel, LPG, LCO, heating oil, and/or jet fuel, from conversion of apetroleum fraction feedstock, comprising processing a petroleum fractionfeedstock with a renewable fuel oil feedstock in the presence of acatalyst.

In certain embodiments, the invention relates a fluidized catalyticcracker apparatus comprising a riser having a petroleum fractioninjection port and a renewable fuel injection port or a riser that hasbeen retro-fitted to add an element to allow for the injection ofrenewable fuel. In certain embodiments, the invention relates a refinerysystem, comprising a first assembly for introduction of a petroleumfraction feedstock; and a second assembly for introduction of arenewable fuel oil feedstock or has been retro-fitted to add the same.In certain embodiments, the invention relates a refinery system,comprising a first assembly for introduction of a petroleum fractionfeedstock; and a second assembly for introduction of a renewable fueloil feedstock into the conversion unit of the refinery or has beenretro-fitted or adapted to add the same.

In certain embodiments, the invention relates to one or more units (forexample a conversion unit) in a refinery system suitable for accepting arenewable fuel oil feedstock, comprising an installed independent portfor introducing the renewable fuel oil feedstock. In certainembodiments, the invention relates to refinery system comprising anadditional or modified riser assembly suitable for accepting therenewable fuel oil, for example an independent port comprising a nozzle;a separate or independent tankage for introducing the renewable fuel oilfeedstock; an installed, re-calibrated, or modified or independentcontrol or control system; and/or an installed live-tap for introducingthe renewable fuel oil feedstock.

In certain embodiments, the invention relates a method of increasingmix-zone temperature in an FCC unit comprising injecting between 0.05-15wt. % renewable fuel oil feedstock via a quench riser system downstream(after) of the introduction of a petroleum fraction feedstock injectionnozzle.

In certain embodiments, the invention relates to a method ofco-processing a renewable fuel oil; that has a carbon content level inthe range of between 35-80 wt. %, on a dry basis moisture-free basisand/or an energy content level of at least 30% of the energy contentcontained in the biomass from which it is derived; and a petroleumfraction feedstock; that comprises a gas oil (GO) feedstock, a vacuumgas oil (VGO) feedstock, a heavy gas oil (HGO) feedstock, a middledistillate feedstock, a heavy-middle distillate feedstock, ahydrocarbon-based feedstock, or combinations thereof; by introducing therenewable fuel oil and the petroleum gas fraction feedstock into aconversion unit wherein they have contact with a catalyst.

In certain embodiments, the invention relates to a fuel (for examplediesel fuel and/or gasoline) producing pathway for generating cellulosicrenewable identification numbers comprising converting a cellulosicfeedstock via rapid thermal processing to form a renewable fuel oil andco-processing a petroleum fraction feedstock with the renewable fuel oilin the presence of a catalyst to produce a cellulosic renewableidentification number-compliant fuel. In certain embodiments, theinvention relates a diesel fuel and/or gasoline producing pathway forgenerating cellulosic renewable identification numbers comprisingthermally converting a renewable [cellulosic] biomass feedstock to forma renewable fuel oil and co-processing a petroleum fraction feedstockwith the renewable fuel oil in a refinery to produce a diesel fueland/or gasoline that complies with a fuel pathway specified in U.S.renewable fuel standard program (RFS) regulations for generating thecellulosic renewable identification number. In certain embodiments, theinvention relates to a fuel producing pathway for generating cellulosicrenewable identification numbers comprising thermally processing acellulosic feedstock via rapid thermal processing to form an unenrichedrenewable fuel oil and processing a petroleum fraction feedstock withthe unenriched renewable fuel oil in a refinery to produce a unit ofdiesel fuel sufficient to generate greater than 0.5 units of acellulosic renewable identification number-compliant fuel.

In certain embodiments, the invention relates to a transportation fuelcomprising a product resulting from the catalytic conversion of amixture comprising greater than 90 wt. % of a petroleum fractionfeedstock and less than 10 wt. % of an unenriched renewable fuel oilfeedstock derived from biomass (for example a cellulosic biomass).

In certain embodiments, the invention relates to a method of preparing acellulosic renewable identification number qualifying-fuel comprising,optionally, forming a renewable fuel oil via rapid thermal processing ofa renewable cellulosic biomass feedstock; injecting greater than 90 wt.% of a petroleum fraction feedstock into a refinery process; injectingless than 10 wt. % of the renewable fuel oil into the refinery processproximate the injection point of the petroleum fraction feedstock; andco-processing the petroleum fraction feedstock and renewable fuel oil toproduce the cellulosic-renewable identification number qualifying-fuel;wherein the renewable fuel oil has a pH of 1.5-6, a solids content ofless than 2.5 wt. %, and a water content of 20-45 wt. %.

In certain embodiments, the invention relates to a method of preparing afuel derived at least in part from a renewable fuel processed through arefinery conversion unit, for example an FCC. In certain embodiments,the invention relates to a method of preparing a fuel derived at leastin part from a renewable fuel having a pH of 1.5-6 and a water contentof 20-45 wt. %, that has been processed through a refinery conversionunit, for example an FCC.

In certain embodiments, the invention relates to a method of producing acombustible fuel via a fuel pathway compliant with U.S. renewable fuelstandard program regulations for generating renewable identificationnumbers, wherein the method comprises thermally convertingcellulosic-based biomass into a renewable fuel oil such that the carboncontent of the renewable fuel oil is less than 60 wt. % and has a pH of1.5-8. In certain embodiments, the invention relates to a method ofproducing a combustible fuel via a fuel pathway compliant with U.S.renewable fuel standard program regulations for generating renewableidentification numbers, wherein the method comprises thermallyconverting cellulosic-based biomass into a renewable fuel oil such thatthe carbon content of the renewable fuel oil is greater than at least 80wt. % of the carbon content of the cellulosic-based biomass. In certainembodiments, the invention relates to a method of producing acombustible fuel via a fuel pathway compliant with U.S. renewable fuelstandard program regulations for generating renewable identificationnumbers, wherein the method comprises thermally convertingcellulosic-based biomass into a renewable fuel oil and co-processing aportion of the renewable fuel oil with greater than 90 wt. % of anon-hydrotreated gas oil feedstock to produce the combustible fuel.

In certain embodiments, the invention relates to a fuel compositionderived at least in part from a petroleum fraction feedstock and arenewable fuel oil feedstock wherein the petroleum feedstock andrenewable fuel oil feedstock have been co-processed in the presence of acatalyst. In certain embodiments, the invention relates to a fluidizedcatalytic cracker product composition derived from a feedstockcomprising a renewable fuel oil.

In certain embodiments, the invention relates to a method of preparing afuel comprising processing a petroleum fraction feedstock with arenewable fuel oil feedstock in the presence of a catalyst wherein theyield of fuel product from the process is equivalent to or greater thanthe yield of fuel product resulting from running the process with norenewable fuel oil feedstock, on an energy input basis of the feedstock.In certain embodiments, the invention related to a method of preparing afuel comprising processing a petroleum fraction feedstock with arenewable fuel oil feedstock in the presence of a catalyst wherein thefuel obtain from the process is completely compatible with fuel derivedwith no renewable fuel oil feedstock.

In certain embodiments, the invention relates to a method of generatingone or more cellulosic-renewable identification numbers comprisingthermally processing a cellulosic biomass to form a renewable fuel oil(for example an unenriched renewable fuel oil) and co-processing apetroleum fraction feedstock with the renewable fuel oil in a refineryconversion unit to thereby produce a cellulosic-renewable identificationnumber-compliant diesel fuel, jet fuel, gasoline, or heating oil.

In certain embodiments, the invention relates to a combustible fuel foran internal combustion engine, derived from a petroleum fractionfeedstock and less than 5 wt. % of a renewable fuel oil feedstockwherein the renewable fuel oil feedstock and the petroleum fractionfeedstock are co-processed in the presence of an FCC catalyst.

In certain embodiments, the invention relates to a method of improvingan amount of valuable fuel components derived from the conversion of apetroleum fraction feedstock comprising introducing the petroleumfraction feedstock into a refinery system comprising an FCC catalyst andadding at least 2 wt. % renewable fuel oil feedstock, relative to thetotal amount feedstock (for example petroleum fraction feedstock plusrenewable fuel oil feedstock) and co-processing, in the presence of theFCC catalyst, the combined feedstock in the FCC for at least 2 seconds.

In certain embodiments, the invention relates to a method of tradingrenewable identification numbers, comprising co-processing petroleumfraction feedstock with a renewable fuel oil to form fuel compliant withone or more fuel pathways, in accordance with the U.S. renewable fuelstandard program, and transferring the rights of at least a portion ofthe one or more U.S. renewable identification numbers from the owner orpurchaser of the fuel. In certain embodiments, the invention relates toa renewable fuel oil compliant with a fuel pathway specified in U.S.renewable fuel standard program regulations for generating thecellulosic renewable identification number, derived by thermallyprocessing cellulosic biomass. In certain embodiments, the inventionrelates to an internal combustion engine fuel derived from a renewablefuel oil compliant with a fuel pathway specified in U.S. renewable fuelstandard program regulations for generating the cellulosic renewableidentification number. In certain embodiments, the invention relates toan internal combustion engine fuel derived from a refinery conversionunit feedstock comprising 1-5 wt % of a renewable fuel oil compliantwith a fuel pathway specified in U.S. renewable fuel standard programregulations for generating the cellulosic renewable identificationnumber.

In certain embodiments, the invention relates to a blended combustiblefuel composition comprising a FCC co-processed gas oil and renewablefuel oil product.

In certain embodiments, the invention relates to a method of using oneor more of the above fuels in a vehicle comprising an internalcombustion engine.

In certain embodiments, the invention relates to a computer systemcomprising monitoring an amount of throughput in an FCC unit andcontrolling the amount of renewable fuel oil to introduce forco-processing with petroleum based feedstock.

In certain embodiments, the invention relates to a computer systemcomprising monitoring an amount of throughput in an FCC unit inclusiveof the quantity of renewable fuel oil being processed and calculatingthe cellulosic-renewable identification numbers generated.

DETAILED DESCRIPTION OF THE DRAWINGS

Many of the benefits of the materials, systems, methods, products, uses,and applications among others may be readily appreciated and understoodfrom consideration of the description and details provided in thisapplication inclusive of the accompanying drawings and abstract,wherein:

FIG. 1: illustrates a fluid catalytic cracking (FCC) unit.

FIG. 2A: illustrates a exemplary converter.

FIG. 2B: illustrates a exemplary converter that has been retro-fittedwith an injection port or two (102), with two different locations (whichmay be alternative locations or both used) suitable for introducing arenewable fuel oil (RFO) feedstock.

FIG. 3: illustrates a riser quench technology.

FIG. 4: illustrates a coking unit.

FIG. 5: illustrates a feed injection system.

FIG. 6: illustrates a FCC unit with dual risers.

FIG. 7: is a graph presenting the influence of catalyst:oil ratio andRFO concentration in VGO on conversion (on a mass basis).

FIG. 8: is a graph presenting the influence of catalyst:oil ratio andRFO concentration in VGO on overall conversion (on an equivalent energyinput basis).

FIG. 9: is a graph presenting the influence of catalyst:oil ratio andRFO concentration in VGO on gasoline yield (on an energy equivalentinput basis).

FIG. 10: is a graph depicting the influence of catalyst:oil ratio andRFO concentration in VGO on gasoline yield as a function of feed carboncontent (on an equivalent carbon input basis).

FIG. 11: is a graph depicting the influence of catalyst:oil ratio andRFO concentration in VGO on LPG yield (on an equivalent energy inputbasis).

FIG. 12: is a graph depicting the influence of catalyst:oil ratio andRFO concentration in VGO on dry gas yield (on an equivalent energy inputbasis).

FIG. 13: is a graph depicting the influence of catalyst:oil ratio andRFO concentration in VGO on LCO yield (on an equivalent energy inputbasis).

FIG. 14: is a graph depicting the influence of catalyst:oil ratio andRFO concentration in VGO on HCO yield (on an equivalent energy inputbasis).

FIG. 15: is a graph depicting the influence of catalyst:oil ratio andRFO concentration in VGO on coke yield (on an equivalent energy inputbasis)).

FIG. 16: is a graph depicting gasoline yield as a function of RFOsubstitution and catalyst:oil ratio (on a 10,000 bbls/day, water freebasis).

FIG. 17: is graph depicting gallons of gasoline/ton of RFO as a functionof RFO substitution and catalyst:oil ratio (on a wt. % contributionusing reference VGO).

FIG. 18: is a graph depicting the influence of catalyst:oil ratio andRFO concentration in VGO on gasoline yield (on volume input to the FCCunit basis).

FIG. 19: is a graph depicting the influence of catalyst:oil ratio andRFO concentration in HGO on gasoline yield (on a 10,000 bbls/day feedbasis)

DETAILED DESCRIPTION

In 2005, the Environmental Protection Agency (EPA) released itsRenewable Fuel Standards (RFS1), which were the first renewable fuelmandates in the United States. The RFS called for 7.5 B gallons ofrenewable fuel to be blended into gasoline by 2012. Two years later, theprogram was expanded under the Energy Independence and Security Act of(EISA) of 2007 to target 36 B gallons of renewable fuel by 2022. Inaddition, EISA expanded the RFS to cover diesel fuels as well asgasoline (jet fuels were not initially included under RFS) andestablished individual volume targets for the different types ofrenewable fuel (e.g., RFS2 calls for 21 B gallons of advanced biofuelsby 2022).

In February 2010, the EPA submitted its final rule for RFS2, itsrevision to the previous renewable fuel standards (RFS1). The ruling setforth volume targets for 36 B gallons of renewable fuels produced in theUS by 2022 with 21 B being advanced biofuels (non-ethanol). Due to thelack of commercial cellulosic facilities in the U.S., the EPA conductsan annual review of total cellulosic capacity to evaluate thefeasibility of its production targets and subsequently makesadjustments. The EPA has proposed cellulosic volumes of up to 12.9Mgallons (up to 15.7M gallons on an ethanol equivalent basis) for 2012,well below its original 500M gallon target. Significant progress must bemade in facilitating the scale-up cellulosic technologies in order forthe U.S. to meet the 16 B gallon production target for cellulosic fuelsby 2022.

Part of the regulations include an incentive program that provides foran award of Renewable Identification Numbers (RIN) for the production offuels in accordance with certain pathways that are designed to beenvironmentally less harmful than the traditional methods of producingfuels. Among the several approved pathways, there are some related tothe use of cellulosic containing biomass (cellulosic biomass) that canearn Cellulosic Renewable Identification Numbers (C-RIN's). The use ofcellulosic biomass can also aid fuel producers in meeting theirRenewable Volume Obligations (RVO) as well. One aspect of the currentapplication may be that the use of unenriched renewable fuel oil inamounts of less than 20 wt. %, for example, less than 10 wt. %, lessthan 8 wt. %, less than 6 wt. % such as at about 5 wt. % or about 3 wt.%; relative to the total weight of feedstock fed (for example, petroleumfraction and renewable feedstock) to a conversion unit employed toproduce gasoline, among other fuels and by products, resulted not onlyin an opportunity to comply with the requirements to earn C-RIN's and/orRVO's but also an at least an equivalent yield of gasoline (on anequivalent input basis, for example, energy basis or carbon contentbasis). The equivalent yield of gasoline includes an increase yield ofgasoline for example and increase of more than 0.5 wt. %, more than 0.75wt. %, more than 1 wt. %, such as from 0.5 wt. % and 5.0 wt. % or from1.25 wt. % and 3.0 wt. % on an equivalent input basis, for example,energy basis or carbon content basis.

In certain embodiments, a method and system for including renewablefuel, renewable fuel oil, or renewable oil as a feedstock in FCCs andother refinery systems or field upgrader operations. Renewable fuelsinclude fuels produced from renewable resources. Examples includebiofuels (e.g. vegetable oil used as fuel), ethanol, methanol frombiomass, or biodiesel and Hydrogen fuel (when produced with renewableprocesses), thermochemically produced liquids, and catalyticallyconverted biomass to liquids.

Suitable biomass, biomass materials, or biomass components, include butare not limited to, wood, wood residues, sawdust, slash bark, thinnings,forest cullings, begasse, corn fiber, corn stover, empty fruit bunches(EFB), fronds, palm fronds, flax, straw, low-ash straw, energy crops,palm oil, non-food-based biomass materials, crop residue, slash,pre-commercial thinnings and tree residue, annual covercrops,switchgrass, miscanthus, cellulosic containing components, cellulosiccomponents of separated yard waste, cellulosic components of separatedfood waste, cellulosic components of separated municipal solid waste(MSW), or combinations thereof. Cellulosic biomass, for example,includes biomass derived from or containing cellulosic materials. Forexample, the biomass may be one characterized as being compliant withU.S. renewable fuel standard program (RFS) regulations, or a biomasssuitable for preparing a cellulosic-renewable identificationnumber-compliant fuel. In certain embodiments, the biomass may becharacterized as being compliant with those biomass materials specifiedin the pathways for a D-code 1, 2, 3, 4, 5, 6, or 7-compliant fuel, inaccordance with the U.S. renewable fuel standard program (RFS)regulations. For example, the biomass may be characterized as beingcompliant with those biomass materials suitable for preparing a D-code 3or 7-compliant fuel, in accordance with the U.S. renewable fuel standardprogram (RFS) regulations or the biomass may be characterized as beingcomposed of only hydrocarbons (or renewable hydrocarbons).

A renewable fuel oil (also referred to herein as “RFO”) refers to abiomass-derived fuel oil or a fuel oil prepared from the conversion ofbiomass. For example, in certain embodiments, the renewable fuel oil maybe a cellulosic renewable fuel oil (also referred to herein as“cellulosic RFO”), and may be derived or prepared from the conversion ofcellulosic-containing biomass. The biomass or cellulosic-containingbiomass may be converted to form a suitable renewable fuel, by one ormore of the following processes: thermal conversion, thermo-mechanicalconversion, thermo-catalytic conversion, or catalytic conversion of thebiomass or cellulosic-containing biomass. In certain embodiments, therenewable fuel oil may be non-hydrodeoxygenated (non-HDO),non-deoxygenated, non-upgraded, thermally-processed, rapidthermally-processed, thermo-mechanically-processed, rapidthermo-mechanically-processed, non-hydrotreated, conditioned, and/orcombinations thereof. For example, the renewable fuel oil may benon-hydrodeoxygenated (non-HDO) renewable fuel oil; a non-HDO,non-deoxygenated renewable fuel oil; a rapidthermo-mechanically-processed, non-hydrotreated renewable fuel oil; or anon-deoxygenated, non-upgraded, thermally-processed renewable fuel oil.A further example of a suitable renewable fuel oil may be anon-hydrodeoxygenated, non-deoxygenated, non-hydrotreated, non-upgraded,non-catalytically processed, thermo-mechanically-processed renewablefuel oil which would be understood to mean a renewable fuel oil that maybe derived from simply mechanically grinding a biomass, for example acellulosic biomass, and then thermally processing the ground biomass,for example rapidly, to derive a liquid with no further processing stepsto substantially alter the oxygen content, the water content, the sulfurcontent, the nitrogen content, the solids content or otherwise enrichthe renewable fuel oil for processing into a fuel. Additionally, thisnon-hydrodeoxygenated, non-deoxygenated, non-hydrotreated, non-upgraded,non-catalytically processed, thermo-mechanically-processed renewablefuel oil could be blended with other batches of non-hydrodeoxygenated,non-deoxygenated, non-hydrotreated, non-upgraded, non-catalyticallyprocessed, thermo-mechanically-processed renewable fuel oil and/or othernon-hydrodeoxygenated, non-deoxygenated, non-hydrotreated, non-upgraded,non-catalytically processed, thermo-mechanically-processed renewablefuel oil that have been derived from other biomass to form blends ofnon-hydrodeoxygenated, non-deoxygenated, non-hydrotreated, non-upgraded,non-catalytically processed, thermo-mechanically-processed renewablefuel oil.

In particular, the renewable fuel oil may be a liquid formed from abiomass comprising cellulosic material, wherein the only processing ofthe biomass may be a therma-mechanical process (specifically comprisinggrinding and rapid thermal processing, with no post processing orenrichment of the liquid prior to introduction into petroleum conversionunit). Specifically, no hydrodeoxygenation, no hydrotreating, nocatalytic exposure or contact just unenriched renewable fuel oil derivedby thermo-mechanically processing cellulosic containing biomass.

A preferred renewable fuel oil may be an unenriched liquid (alsoreferred to as an unenriched renewable fuel oil) formed from ground-upbiomass by a process, for example rapid thermal processing, wherein theresulting liquid may be at least 50 wt. %, for example at least 60 wt.%, at least 70 wt. %, at least 75 wt. %, at 80 wt. % or at least 85 wt.% of the total weight of the processed biomass. In other words theliquid yield from the processed biomass may be at least 50 wt. %, forexample at least 60 wt. %, at least 70 wt. %, at least 75 wt. %, at 80wt. % or at least 85 wt. % of the total weight of the ground biomassbeing processed. Unenriched should be understood to refer to renewablefuel oil liquid that does not undergo any further pre- orpost-processing including, specifically, no hydrodeoxygenation, nohydrotreating, no catalytic exposure or contact. In certain embodiments,unenriched renewable fuel oil may be prepared from the ground biomassand then transported and/or stored, and may be even heated or maintainedat a given temperature; not exceeding 150 degrees Fahrenheit, on its wayto being introduced into the coversion unit at the refinery. Themechanical handling associated with transporting, storing, heating,and/or pre-heating of the unenriched renewable fuel oil is not beconsidered an enriching step. In certain embodiments, an unenrichedrenewable fuel oil may comprise one or more unenriched renewable fuelsoils mixed from separate unenriched batches and/or unenriched batchesresulting from different cellulosic biomass (for example, severaldifferent types of non-food biomass). In certain embodiments, thesemixed compositions, which may be blended to purposefully provide orachieve certain characterisitics in the combined unenriched renewablefuel oil, may still be considered unenriched renewable fuel oil providedthat substantially all (for example greater than 80 wt. %, or greaterthan 90 wt. % such as greater than 95 wt. % or greater than 98 wt. % orgreater than 99 wt. %) or all of the combined batches are unenrichedrenewable fuel oil.

A preferred (non-HDO) renewable fuel oil; a non-HDO, non-deoxygenatedrenewable fuel oil; a rapid thermo-mechanically-processed,non-hydrotreated renewable fuel oil; or a non-deoxygenated,non-upgraded, thermally-processed renewable fuel oil.

For example, the renewable fuel oil may comprise only thermallyconverted biomass or only thermo-mechanically converted biomass.Suitable renewable fuel oils may include a pyrolytic liquid, athermo-pyrolytic liquid, a thermo-mechanical-pyrolytic liquid, a rapidthermo-pyrolytic liquid, or a rapid thermo-pyrolytic-mechanical liquid,derived or prepared from the conversion of biomass or cellulosicbiomass. In certain embodiments, the renewable fuel oil may include anon-hydrodeoxygenated (non-HDO) renewable fuel oil; a non-deoxygenatedrenewable fuel oil; a non-upgraded renewable fuel oil; athermally-processed cellulosic renewable fuel oil; athermally-processed, non-upgraded-cellulosic renewable fuel oil; athermally-processed biomass liquid; a thermally-processed,non-upgraded-biomass liquid; a thermally processed non-food-basedbiomass liquid; a thermally-processed non-food, cellulosic-based biomassliquid; a thermally-processed non-food, renewable liquid; athermally-processed cellulosic liquid; a rapid thermal-processedcellulosic liquid; a rapid thermal-processed bio-oil; a rapid thermalprocessed biomass liquid or thermo-pyrolytic liquid having less than 5wt. % solid content, such as less than 4 wt. %, 3 wt. %, 2.5 wt. %, 2wt. %, 1 wt. %, or less than 0.5 wt. % solid content; a conditionedrenewable fuel oil; a non-hydrotreated, non-upgraded renewable fuel oil;a pyrolysis oil or pyrolytic liquid; a thermo-pyrolysis oil or athermo-pyrolytic liquid; a biooil or a bio-oil liquid; a biocrude oil orbiocrude liquid; a thermo-catalytic pyrolysis oil or a thermo-catalyticpyrolytic oil; a catalytic pyrolysis oil; a catalytic pyrolytic liquid;or combinations thereof. For example, in certain embodiments, therenewable fuel oil may comprise one or more of a non-hydrodeoxygenated(non-HDO) renewable fuel oil; a non-deoxygenated renewable fuel oil; anon-upgraded renewable fuel oil; a thermally-processed cellulosicrenewable fuel oil; a rapid thermo-mechanically-processed renewable fueloil; a non-hydrotreated, non-upgraded renewable fuel oil; a pyrolysisoil or pyrolytic liquid; or a thermo-pyrolysis oil or a thermo-pyrolyticliquid.

In certain embodiments, the thermal conversion process of forming asuitable renewable fuel from biomass may include, for example, rapidthermal conversion processing. In certain embodiments, the mechanicalaspect of the conversion process (sometimes referred to herein as“conditioning”), of forming a suitable renewable fuel from biomass mayinclude, but may be not limited to drying; grinding; removing fines;removing tramp metal; sizing; removing ferrous metals; removing portionsof ash; filtering; screening; cycloning; mechanically manipulating toremove a substantial portion of solid content; or combinations thereof.For example, conditioning may include one or more of the followingprocesses, such as drying, grinding, removing fines, removing trampmetal, sizing, removing ferrous metals, removing portions of ash,filtering, screening, passing through a cyclone, mechanicallymanipulating, contacting with a magnet, or passing through a magneticfield. In certain embodiments, the conditioning may further include theaddition of water or one or more alcohols, such as methanol, ethanol,propanol, isopropyl alcohol, glycerol, or butanol. For example, therenewable fuel oil may be conditioned by undergoing filtering,screening, cycloning, or mechanical manipulation processes to remove asubstantial portion of solid content. In certain embodiments,conditioning of the biomass during the conversion to form a suitablerenewable fuel oil may include removing a portion of carbon from thebiomass by filtering, screening, cyclone, or mechanically manipulatingthe biomass. In certain embodiments, the thermal conversion process orthermo-mechanical conversion process may comprise a rapid thermalconversion process.

In certain embodiments, the renewable fuel oil may have a pH in therange of 0.5 to 8.0. For example, the renewable fuel oil may have a pHin the range of 0.5 to 7.0, such as 0.5 to 6.5, 1.0 to 6.0, 2.0 to 5.0,3.0 to 7.0, 1.0 to 4.0, or 2.0 to 3.5. In certain embodiments, the pH ofthe renewable fuel oil may be less than 8.0, such as less than 7.0, lessthan 6.5, less than 6.0, less than 5.5, less than 5.0, less than 4.5,less than 4.0, less than 3.5, less than 3.0, less than 2.5, or less than2.0. In certain embodiments, the pH of the renewable fuel oil may bealtered or modified by the addition of an external, non-biomass derivedmaterial or pH altering agent. In certain embodiments, the renewablefuel oil may be acidic. For example, the renewable fuel oil may have apH in the range of between 0.5 to 7, such as between 1 to 7, between 1to 6.5, between 2 to 5. between 2 to 3.5, between 1 to 4, between 2 to6, or between 2 to 5. In certain embodiments, the renewable fuel oil hasthe pH resulting from the conversion of the biomass from which it may bederived, such as a biomass-derived pH.

In certain embodiments, the renewable fuel oil may have a solids contentin the range less than 5 wt. %. For example, the renewable fuel oil mayhave a solids content of less than 4 wt. %, less than 3 wt. %, less than2.5 wt. %, less than 2 wt. %, less than 1 wt. %, less than 0.5 wt. %, orless than 0.1 wt. %. In certain embodiments, the renewable fuel oil mayhave a solids content in the range of between 0.005 wt. % and 5 wt. %.For example, the renewable fuel oil may have a solids content in therange of between 0.005 wt. % and 4 wt. %, such as between 0.005 wt. %and 3 wt. %, between 0.005 wt. % and 2.5 wt. %, between 0.005 wt. % and2 wt. %, between 0.005 wt. % and 1 wt. %, between 0.005 wt. % and 0.5wt. %, between 0.05 wt. % and 4 wt. %, between 0.05 wt. % and 2.5 wt. %,between 0.05 wt. % and 1 wt. %, between 0.05 wt. % and 0.5 wt. %,between 0.5 wt. % and 3 wt. %, between 0.5 wt. % and 1.5 wt. %, orbetween 0.5 wt. % and 1 wt. %.

In certain embodiments, the renewable fuel oil may have an ash contentof less than 0.5 wt. %. For example, the renewable fuel oil may have anash content of less than 0.4 wt. %, such as less than 0.3 wt. %, lessthan 0.2 wt. %, less than 0.1 wt. %, less than 0.05 wt. %, less than0.005 wt. %, or less than 0.0005 wt. %. In certain embodiments, therenewable fuel oil may have an ash content in the range of between0.0005 wt. % and 0.5 wt. %, such as between 0.0005 wt. % and 0.2 wt. %,between 0.0005 wt. % and 0.05 wt. %, or between 0.0005 wt. % and 0.1 wt.%.

In certain embodiments, the renewable fuel oil may comprise a watercontent in the range of between 10-40 wt. %. For example, the renewablefuel oil may comprise a water content in the range of between 15-35 wt.%, such as between 15-30 wt. %, between 20-35 wt. %, between 20-30 wt.%, between 30-35 wt. %, between 25-30 wt. %, or between 32-33 wt. %water. In certain embodiments, the renewable fuel oil may comprise awater content in the range of less than 40 wt. %, such as less than 35wt. %, or less than 30 wt. %. In certain embodiments, the renewable fueloil may comprise a water content of at least 10 wt. %, such as at least15 wt. %, at least 20 wt. %, or at least 25 wt. %.

In certain embodiments, the renewable fuel oil may comprise an oxygencontent level higher than that of a petroleum fraction feedstock. Forexample, the renewable fuel oil may have an oxygen content level ofgreater than 20 wt. %, on a dry basis or moisture-free basis, such as anoxygen content level in the range of between 20-50 wt. %, between 35-40wt. %, between 25-35 wt. %, between 20-30 wt. %, between 25-50 wt. %,between 20-40 wt. %, or between 20-35 wt. %, on a dry basis ormoisture-free basis.

In certain embodiments, the renewable fuel oil may comprise a greateroxygen content level than carbon content level. For example, therenewable fuel oil may have a greater oxygen content level than carboncontent level, on a moisture-containing basis. In certain embodiments,the renewable fuel oil may have in the range of between 35-80 wt. %carbon content and in the range of between 20-50 wt. % oxygen content,on a dry basis or moisture-free basis. For example, the renewable fueloil may have in the range of between 50-60 wt. % carbon content and inthe range of between 35-40 wt. % oxygen content, on a dry basis ormoisture-free basis.

In certain embodiments, the renewable fuel oil may comprise a carboncontent level of at least 40 wt. % of the carbon content contained inthe biomass from which it may be derived. For example, the renewablefuel oil may comprise a carbon content level of at least 45 wt. %, suchas at least 50 wt. %, at least 55 wt. %, at least 60 wt. %, at least 65wt. %, at least 70 wt. %, at least 75 wt. %, at least 80 wt. %, at least85 wt. %, at least 90 wt. %, or at least 95 wt. % of the carbon contentcontained in the biomass from which it may be derived. In certainembodiments, the renewable fuel oil may comprise a carbon content levelin the range of between 40 wt. % and 100 wt. % of the carbon contentcontained in the biomass from which it may be derived. For example, therenewable fuel oil may comprise a carbon content level in the range ofbetween 40 wt. % and 95 wt. %, between 40 wt. % and 90 wt. %, between 40wt. % and 80 wt. %, between 50 wt. % and 90 wt. %, between 50 wt. % and75 wt. %, between 60 wt. % and 90 wt. %, between 60 wt. % and 80 wt. %,between 70 wt. % and 95 wt. %, between 70 wt. % and 80 wt. %, or between70 wt. % and 90 wt. % of the carbon content contained in the biomassfrom which it may be derived. In certain embodiments, the renewable fueloil may comprise a carbon content level lower than that of a petroleumfraction feedstock. For example, the renewable fuel oil may comprise acarbon content level in the range of between 35-80 wt. %, on a dry basismoisture-free basis, such as between 40-75 wt. %, between 45-70 wt. %,between 50-65 wt. %, between 50-60 wt. %, or between 54-58 wt. %, on adry basis or moisture-free basis.

By way of example, Tables 1&2 provide analyses of several suitablerenewable fuel oils which were prepared according to one or more of theprocedures described in U.S. Pat. No. 7,905,990, U.S. Pat. No.5,961,786, and U.S. Pat. No. 5,792,340, each of which is incorporated byreference in their entirety.

TABLE 1 Analytical Results for Alcell Lignin - Mild Run (LS-3) & SevereRun (LS-4) LS-3 LS-4 Volatiles (wt %) 14.7 27.9 Moisture Content (wt %)1.0 0.9 Ash content (wt %) 0.05 1.00 Elemental (wt %, MAF) Carbon 68.6873.04 Hydrogen 7.16 6.52 Nitrogen 0.00 0.01 Oxygen (difference) 24.1620.43 Hydroxyl (wt %) 7.54 7.50 Methoxyl (wt %) 15.68 1.02 SequentialSolubility (wt %) Diethyl Ether 41.8 40.3 Ethyl Acetate 48.9 42.4Methanol 0.2 0.6 Residue 9.1 16.7 Fractionation (wt %) Organic Acids31.7 3.6 Phenols & Neutrals 45.0 81.7 Residue 23.3 14.1 TABLE NOTE: MildRun (LS-3) was rapid thermal processed at about 500° C. and the SevereRun (LS-4) was rapid thermal processed ar about 700° C.

TABLE 2 Analytical Results of Renewable Fuel Oil Derived from WoodBiomass LABORATORY 1) 1) 2) 3) 3) 4) 5) AVERAGE SPECIFIC 1.19 1.20 1.211.217 1.226 1.186 1.188 1.20 GRAVITY WATER CONTENT 26 27 21 20.5 21 28.123.9 (% by wt) CHAR CONTENT 2.0 0.6 1.4 2.2 5.5 2.2 2.3 (% by wt) HIGHERHEATING 7267 7310 9245 7525 7955 6536 6880 7525 (BTU/lb) ELEMENTAL (%,MAF) CARBON 55.1 53.63 55.5 52.8 58.27 51.5 54.5 HYDROGEN 6.7 6.06 6.76.9 5.5 6.8 6.4 NITROGEN 0.15 0.24 0.1 <0.1 0.39 0.17 0.18 SULFUR 0.02<0.14 0.07 <.001 ASH (% by wt) 0.13 0.15 0.22 0.13 0.16 TABLE NOTES: TheRFO derived from the Wood Biomass was analyzed by the following labs: 1)Universite Catholique de Louvain, Belgium; 2) ENEL, Centro RicercaTermica, Italy; 3) VTT, Laboratory of Fuel and Process Technology,Finland; 4) CANMET, Energy Research Laboratories, Canada; 5) CommercialTesting and Engineering Co., U.S.A.

In certain embodiments, the renewable fuel oil may comprise an energycontent level of at least 30% of the energy content contained in thebiomass from which it may be derived. For example, the renewable fueloil may comprise a energy content level of at least 45%, such as atleast 55. %, at least 60%, at least 65. %, at least 70. %, at least 75.%, at least 80. %, at least 85%, at least 90. %, or at least 95. % ofthe energy content contained in the biomass from which it may bederived. In certain embodiments, the renewable fuel oil may comprise aenergy content level in the range of between 50% and 98% of the energycontent contained in the biomass from which it may be derived. Forexample, the renewable fuel oil may comprise a energy content level inthe range of between 50% and 90%, between 50% and 75%, between 60% and90%, between 60% and 80%, between 70% and 95%, between 70% and 80%, orbetween 70% and 90% of the energy content contained in the biomass fromwhich it may be derived.

In certain embodiments, the renewable fuel oil may comprise a energycontent level lower than that of a petroleum fraction feedstock. Forexample, the renewable fuel oil may comprise a energy content level inthe range of between 30-95%, on a dry basis (moisture-free basis),relative to the energy content of a petroleum feedstock, such as between40-90%, between 45-85%, between 50-80%, between 50-60%, or between54-58%, on a dry basis or moisture-free basis, relative to the energycontent of a petroleum feedstock. In certain embodiments, the renewablefuel oil may have an energy content in the range of between 30-90%,relative to the petroleum fraction feedstock energy content. Forexample, the renewable fuel oil may have an energy content of 35%, 40%,45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, relative to the petroleumfraction feedstock energy content. In certain embodiments, a unit of therenewable fuel oil may have an energy content suitable to generatebetween 0.5-1.5 units of cellulosic-renewable index number-compliantfuel, such as between 0.7-1.2 units, between 0.9-1.1 units ofcellulosic-renewable index number-compliant fuel. In certainembodiments, a unit of the renewable fuel oil may have an energy contentequivalent to between 0.5-1.5 volume units of ethanol, such as between0.7-1.2 volume units, between 0.9-1.1 volume units of ethanol.

In certain embodiments, a refinery method and system may include anassembly for introducing renewable fuel, renewable fuel oil orbiomass-derived thermally produced liquid, in low proportions into apetroleum conversion unit, a refinery FCC unit (know more formally as afluidized catalytic cracker) or field upgrader operation with thecontact time of the FCC catalyst being for a period of seconds, forexample 0.5 to 15 seconds, such as 1 second, 1.5 seconds, 2 seconds, 2.5seconds, 3 seconds, 3.5 seconds, 4 seconds, 5 seconds and time periodsapproximating these times for example approximately 3-5 seconds.

The renewable oil may be conditioned to enable introduction into therefinery process and can be made from several compositions. One suchexample may be renewable oil that was produced from the rapid thermalconversion of biomass under the conditions of 400 to 600° C. at aprocessing residence time of less than 10 seconds either with or withoutthe action of a catalyst. An example of a catalyst may be ZSM-5 or otherFCC catalyst.

According to one embodiment, an amount of thermally produced renewableoil addition rate (in the case of an FCC unit, an example detailed inFIG. 1) includes less than 10% by weight (e.g. in a range between 0.05%by weight and 10% by weight), preferably in the range greater than 1% byweight and less than 5% by weight.

In certain embodiments, a petroleum fraction feedstock, for examplederived from upgrading petroleum, comprises a gas oil (GO) feedstock, avacuum gas oil (VGO) feedstock, a heavy gas oil (HGO) feedstock, amiddle distillate feedstock, a heavy-middle distillate feedstock, ahydrocarbon-based feedstock, or combinations thereof. For example, thepetroleum fraction feedstock comprises a gas oil feedstock, a vacuum gasoil (VGO) feedstock, a heavy gas oil (HGO) feedstock, or a middledistillate feedstock.

In certain embodiments, the amount of renewable fuel oil (RFO) feedstockthat may be introduced into a refinery for co-processing with apetroleum fraction feedstock, may be in the range of 1 wt. % to 20 wt.%, relative to the total amount of feedstock introduced into therefinery for processing. For example, the amount of renewable fuel oil(RFO) feedstock introduced into the refinery for co-processing with apetroleum fraction feedstock, may be in the range of 1 wt. % to 15 wt.%, relative to the total amount (for example the petroleum fractionfeedstock plus the RFO feedstock) of feedstock introduced into theconversion unit of the refinery for processing, such as 2 wt. % to 13wt. %, 4 wt. % to 10 wt. %, 5 wt. % to 8 wt. %, 7 wt. % to 12 wt. %, or3 wt. % to 7 wt. %, relative to the total amount of feedstock introducedinto the conversion unit for processing. In certain embodiments, theamount of renewable fuel oil (RFO) feedstock introduced into theconversion unit for co-processing with a petroleum fraction feedstock,may be 1 wt. %, relative to the total amount of feedstock introducedinto the refinery for processing, such as 2 wt. %, 3 wt. %, 4 wt. %, 5wt. %, 6 wt. %, 7 wt. %, 8 wt. %, 9 wt. %, 10 wt. %, 11 wt. %, 12 wt. %,13 wt. %, 14 wt. %, 15 wt. %, 16 wt. %, 17 wt. %, 18 wt. %, 19 wt. %, 20wt. %, relative to the total amount of feedstock introduced into therefinery for processing. In certain embodiments, the amount of renewablefuel oil (RFO) feedstock introduced into the refinery for co-processingwith a petroleum fraction feedstock, may be at least 1 wt. % and lessthan 20 wt. %, relative to the total amount of feedstock introduced intothe refinery for processing, such as at least 2 wt. %, 3 wt. %, 4 wt. %,5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, 9 wt. %, or 10 wt. %, and less than20 wt. %, relative to the total amount of feedstock introduced into theconversion unit for processing.

In certain embodiments, the processing of the petroleum fractionfeedstock with the renewable fuel oil has a substantially equivalent orgreater performance in preparing the fuel product, relative toprocessing solely the petroleum fraction feedstock in the absence of therenewable fuel oil. For example, processing a up to 20 wt. % of RFO withthe remainder petroleum fraction feedstock, for example 2:98, 5:95,10:90 weight ratio of renewable fuel oil to the petroleum fractionfeedstock may have a substantially equivalent or greater performance inthe resulting the fuel products, relative to processing solely thepetroleum fraction feedstock in the absence of the renewable fuel oil.For example, processing in the range of between a 20:80 to 0.05:99.95weight ratio of renewable fuel oil with petroleum fraction feedstock mayresulting in an weight percent increase in gasoline of more than 0.1 wt.%, for example 0.5 wt. %, 1.0 wt. %, 1.5 wt. %, 2.0 wt. % or more,relative to processing solely the petroleum fraction feedstock in theabsence of the renewable fuel oil.

According to one embodiment, an amount of RFO may be blended with a widevariety of gas oils and/or blends of gas oils including HGO (Heavy GasOil), LGO (Light Gas Oil) and VGO (Vacuum Gas Oil) as well as otherpetroleum fractions and blends. The HGO may be another lighter feedstockthat can be directed to a refinery FCC unit. Either in combination withthe gas oil, as in a mixed feed stream or as a separate feed streameither before, after or before and after the introduction of the gasoil. Alternatively, the gas oil may be introduced jointly with the RFO,before, after or before and after the introduction of the RFO. Eitherthe RFO or the gas oil or both may be alternatively fed in a pulsemanner.

According to one embodiment, an amount of renewable oil may be blendedwith VGO (Vacuum Gas Oil). VGO may be a feedstock typically fed to arefinery FCC unit. The blend of renewable oil and VGO targets a finalmeasured TAN (Total Acid Number) less than 1.0 (e.g. in a range between0.05 and 1.0), and preferably in the range less than 0.5 (e.g. in arange between 0.05 and 0.5), and more preferably in the range less than0.25 (e.g. in a range between 0.05 and 0.25).

According to one embodiment, an amount of renewable oil may be blendedwith HGO (Heavy Gas Oil). HGO may be another lighter feedstock that canbe directed to a refinery FCC unit. Either in combination with VGO or asa separate feed.

According to one embodiment, an amount of renewable oil may be blendedwith lighter petroleum fractions such as LCO, or gasoline with orwithout a surfactant. The content of LCO, and/or gasoline blended withthe renewable oil may be in the range of less than 10% by weight (e.g.,in a range between 0.005% by weight and 10% by weight), and preferablyin the range less than 5% by weight (e.g., in a range between 0.005% byweight and 5% by weight), and more preferably in the range of less than1% by weight (e.g., in a range between 0.005% by weight and 1% byweight).

According to one embodiment, the renewable oil includes all of the wholeliquid produced from the thermal or catalytic conversion of biomass,with preferably low water content. Alternatively, whole liquid producedfrom the thermal or catalytic conversion of biomass may be phaseseparated to provide a predominately non-aqueous fraction as thefeedstock for refinery systems. In addition, fractions can be taken fromthe unit operations of the downstream liquid collection system ofthermal or catalytically converted biomass such as a primary condensermeans, a secondary condenser, demister, filter, or an electrostaticprecipitator.

According to one embodiment, the flash point of a renewable oil may beincreased to reduce the volatile content of the liquid and subsequentlyco-processed in an FCC with a petroleum feedstock. The flash point wouldbe increased above the range of 55-62° C. as measured by thePensky-Martens closed cup flash point tester (e.g. ASTM D-93). Variousmethods and apparatus can be used to effectively reduce the volatilecomponents, such as wiped film evaporator, falling film evaporator,flash column, packed column, devolatilization vessel or tank. Reductionof the some of the volatile components of the renewable can help toreduce undesirable components such as phenols from passing through theFCC reactor and ending up in the collected water stream.

In certain embodiments, the water content of the renewable fuel oil(RFO) feedstock that may be introduced into a refinery for co-processingwith a petroleum fraction feedstock, may be in the range of 0.05 wt. %to 40 wt. %. For example, the water content of the renewable fuel oil(RFO) feedstock introduced into the refinery for co-processing with apetroleum fraction feedstock, may be in the range of 1 wt. % to 35 wt.%, such as 5 wt. % to 35 wt. %, 10 wt. % to 30 wt. %, 10 wt. % to 20 wt.%, 10 wt. % to 15 wt. %, 15 wt. % to 25 wt. %, 15 wt. % to 20 wt. %, 20wt. % to 35 wt. %, 20 wt. % to 30 wt. %, 20 wt. % to 25 wt. %, 25 wt. %to 30 wt. %, or 30 wt. % to 35 wt. %. In certain embodiments, the watercontent of the renewable fuel oil (RFO) feedstock introduced into therefinery for co-processing with a petroleum fraction feedstock, may beat least 23 wt. % such as at least 25 wt. %, at least 28 wt. %, at least30 wt. %, at least 31 wt. %, at least 32 wt. %, at least 33 wt. %, or atleast 35 wt. %. In certain embodiments, the water content of therenewable fuel oil (RFO) feedstock introduced into the refinery forco-processing with a petroleum fraction feedstock, may be at least 1 wt.%, such as at least 10 wt. %, at least 15 wt. %, at least 20 wt. %, orat least 30 wt. %. In certain embodiments, the water content of therenewable fuel oil (RFO) feedstock introduced into the refinery forco-processing with a petroleum fraction feedstock, may be less than 38wt. %, such as less than 35 wt. %, less than 34 wt. %, less than 30 wt.%, less than 25 wt. %, less than 20 wt. %, or less than 15 wt. %.

The hydrogen forms of zeolites used in FCC systems are powerfulsolid-based acids, and can facilitate a host of acid-catalyzedreactions, such as isomerisation, alkylation, and cracking. The specificactivation modality of most zeolitic catalysts used in petrochemicalapplications involves quantum-chemical Lewis acid site reactions. Thepresent system benefits from the characteristics of renewable oil,namely its TAN or acidic nature, that can lead to an improvement incracking or the conversion of VGO (i.e., a synergistic effect) in FCCoperations. This results in a shift toward more light ends or desirableproducts and a reduction in undesirable products by way of example heavycycle oil and clarified slurry oil.

Fluid catalytic cracking (FCC) may be a conversion process used inpetroleum refineries. It may be widely used to convert the high-boiling,high-molecular weight hydrocarbon fractions of petroleum crude oils tomore valuable gasoline, olefinic gases, and other products. Catalyticcracking produces more gasoline with a higher octane rating. It alsoproduces byproduct gases that are more olefinic, and hence morevaluable, than those produced by thermal cracking.

The feedstock to an FCC may be usually that portion of the crude oilthat has an initial boiling point of 340° C. or higher at atmosphericpressure and an average molecular weight ranging from about 200 to 600or higher. This portion of crude oil may be often referred to as heavygas oil. The FCC process vaporizes and breaks the long-chain moleculesof the high-boiling hydrocarbon liquids into much shorter molecules bycontacting the feedstock, at high temperature and moderate pressure,with a fluidized powdered catalyst.

FIG. 1 illustrates a fluid catalytic cracking (FCC) unit. The schematicflow diagram of a typical modern FCC unit in FIG. 1 is based upon a“side-by-side” configuration. The illustration depicts where therenewable fuel oil feedstock 101 could be introduced into a system. TheFFC could be designed to have two or more feedstock injection points atleast one for the petroleum fraction feedstock and at least one for therenewable fuel oil feedstock or these feedstock could be co-injected (byhave them mixed upstream of the injection point) or the system could befitted with multiple points of injection for either, both or mixtures ofthe feedstock. Alternatively, the FCC unit could be retro-fitted toinclude a way of introducing the renewable fuel oil, for example addingan injection port proximate the riser or at some point in the processwherein the catalyst may be upflowing.

In FIGS. 2A&B, unprocessed renewable oil feedstock 101 can be fedupstream or downstream of a gas oil (GO) feed inlet port 201. Renewableoil feedstock 101 is introduced in this section of the riser therebypotentially imparting properties of the renewable oil (e.g., acid natureof the oil) onto the catalyst and promoting GO conversion as it may beintroduced downstream of the renewable oil 101. Alternatively, therenewable oil can be introduced downstream of the GO fresh feedinjection nozzles 201. FIG. 2B, presents a retrofitted riser with aretro-fitted renewable oil feedstock injection port or ports 102. Theriser may be adapted to include multiple renewable oil feedstockinjection port or ports 102 both before and after the introduction ofthe VGO. It may be retro-fitted to have only one additional renewableoil feedstock injection port 102 positioned either before or after theGO injection point or it may be retro-fitted to have a renewable oilfeedstock injection port or ports 102 along the GO feedstock feed line.

In FIG. 3 A riser quench system injects vaporizable oil into the riserabove the VGO feed injection nozzles 201. The recycle material may actas a heat sink as it may be vaporized by the catalyst. At constant riseroutlet temperature, quench may increase the catalyst-to-oil ratiobecause the riser outlet temperature control point may be downstream ofthe quench location. Introduction of the quench oil may also increasesthe temperature in the mix zone and lower section of the riser, as shownin FIG. 3. In an embodiment (or a retro-fitted embodiment) the renewablefuel oil feedstock may be injected into the quench line of the riser.

In some embodiment, it may be that the primary contaminants found inVGO, typically fed to an FCC, are vanadium, nickel and to a lesserdegree, sodium and iron. The catalyst used in FCC may tend to absorbthese contaminants which may then have a negative effect on theconversion of VGO in the reactor. An additional advantage of co-feedinga renewable fuel oil with a GO, for example VGO, to an FCC may be thatthe renewable oil contains little or none of these contaminants.Thereby, prolonging the useful life of the catalyst, and helping tomaintain greater catalyst activity and improved conversion levels.

In certain embodiments, the system or apparatus may be employed forprocessing or co-processing the petroleum fraction feedstock, therenewable fuel oil, or combinations thereof, may include a refinerysystem, a conversion unit, such as a fluidized catalytic cracker (FCC),a FCC refinery system, a coker, a coking unit, a field upgrader unit, ahydrotreater, a hydrotreatment unit, a hydrocracker, a hydrocrackingunit, or a desulfurization unit. For example, the system, apparatus orconversion may be or comprise an FCC unit operation; the system orapparatus is or comprises a coker; the system or apparatus is orcomprises a hydrotreater; or the system or apparatus is or comprises ahydrocracker. In certain embodiments, the system or apparatus may beemployed for processing or co-processing the petroleum fractionfeedstock, the renewable fuel oil, or combinations thereof, may includea retro-fitted refinery system, such as a refinery system comprising aretro-fitted port for the introduction of a renewable fuel oil. Forexample, the system or apparatus employed may include a retro-fitted FCCrefinery system having one or more retro-fitted ports for introducing arenewable fuel oil. The retro-fitted port, for example, may be stainlesssteel port, such as a 304 or 316 stainless steel port, titanium or someother alloy or combination of high durability, high corrosiveenvironment material.

In certain embodiments, the system present includes an apparatus, and amethod of using the same, for example a refinery system, such as afluidized catalytic cracker (FCC), a FCC refinery system, a coker, acoking unit, a field upgrader unit, a hydrotreater, a hydrotreatmentunit, a hydrocracker, a hydrocracking unit, a desulfurization unit, or aretro-fitted refinery system, in conjunction with providing, injecting,introducing, or processing the renewable fuel oil. For example, arefinery system for processing a petroleum fraction feedstock with arenewable fuel may include a retro-fitted refinery system, a fluidizedcatalytic cracker (FCC), a retro-fitted FCC, a coker, a retro-fittedcoker, a field upgrader unit, a hydrotreater, a retro-fittedhydrotreater, a hydrocracker, or a retro-fitted hydrocracker.

In certain embodiments, the method may include introducing, injecting,feeding, co-feeding, a renewable fuel oil into a refinery system via amixing zone, a nozzle, a retro-fitted port, a retro-fitted nozzle, avelocity steam line, or a live-tap. For example, the method may compriseprocessing a petroleum fraction feedstock with a renewable fuel oil. Incertain embodiments, the processing may comprise co-injecting thepetroleum fraction feedstock and the renewable fuel oil, such asco-feeding, independently or separately introducing, injecting, feeding,or co-feeding, the petroleum fraction feedstock and the renewable fueloil into a refinery system. For example, the petroleum fractionfeedstock and the renewable fuel oil may be provided, introduced,injected, fed, or co-fed proximate to each other into the reactor,reaction zone, reaction riser of the refinery system. In certainembodiments, the renewable fuel oil may be provided, introduced,injected, fed, co-fed into the reactor, reaction zone, or reaction riserof the refinery system proximate, upstream, or downstream to thedelivery or injection point of the petroleum fraction feedstock. Incertain embodiments, the petroleum fraction feedstock and the renewablefuel oil come in contact with each other upon introduction, delivery,injection, feeding, co-feeding into the refinery system, into thereactor, into the reaction zone, or into the reaction riser. In certainembodiments, the petroleum fraction feedstock and the renewable fuel oilcome in contact with each other subsequent to entering the refinerysystem, the reactor, the reaction zone, or the reaction riser. Incertain embodiments, the petroleum fraction feedstock and the renewablefuel oil make first contact with each other subsequent to entering into,introduction into, injection into, feeding into, or co-feeding into therefinery system, the reactor, the reaction zone, or the reaction riser.In certain embodiments, the petroleum fraction feedstock and therenewable fuel oil are co-blended prior to injection into the refinerysystem.

The petroleum fraction feedstock and the renewable fuel oil may beintroduced into the refinery system through different or similardelivery systems. For example, the petroleum fraction feedstock and therenewable fuel oil may be introduced into the refinery system throughone or more independent or separate injection nozzles. The petroleumfraction feedstock and the renewable fuel oil may be introduced into therefinery system proximate or near to each other in a FCC reactor riserin the refinery system. The renewable fuel oil may be introduced intothe refinery system above, below, near, or proximate the introductionpoint of the fossil fuel feedstock in the refinery system. In certainembodiments, one or more injection nozzles may be located in a FCCreactor riser in the refinery system suitable for introducing the fossilfuel feedstock or the renewable fuel oil. The renewable fuel oil may beintroduced into the refinery system through a lift steam line located atthe bottom of the FCC reactor riser. In certain embodiments, thepetroleum fraction feedstock may be introduced into the refinery systemat a first injection point and the renewable fuel oil may be introducedinto the refinery system at a second injection point. For example, thefirst injection point may be upstream of the second injection point, thefirst injection point may be downstream of the second injection point,the first injection point may be proximate to the second injectionpoint, the first injection point and the second injection point may belocated in a reactor riser, such as an FCC reactor riser. In certainembodiments, a renewable fuel oil may be introduced below a reactorriser, such as an FCC reactor riser, during conversion of the petroleumfraction feedstock. For example, a renewable fuel oil may be injectedvia a quench riser system upstream, downstream, or proximate, from theintroduction point of the petroleum fraction feedstock. In certainembodiments, a renewable fuel oil may be injected via a quench risersystem located above, below, or proximate, a petroleum fractionfeedstock injection nozzle.

In certain embodiments, the prepared fuel product may comprise a productof a fluidized catalytic cracker having a petroleum fraction and arenewable fuel oil as reactants, for example, a product of a fluidizedcatalytic cracker processing a petroleum fraction and a renewable fueloil, a product of a fluidized catalytic cracker wherein the fluidizedcatalytic cracker receives a petroleum fraction and a renewable fueloil, a processed product from a mixture of a petroleum fractionfeedstock and a renewable fuel oil that have been in contact with acatalyst.

In certain embodiments, the prepared fuel product may comprise afluidized catalytic cracker product composition derived from catalyticcontact of a feedstock comprising a renewable fuel oil, for example afuel composition derived from a petroleum fraction feedstock, and arenewable fuel oil feedstock, such as a fuel composition derived from80-99.95 wt. % of a petroleum fraction feedstock, and 0.05-20 wt. % of arenewable fuel oil feedstock, or a fuel composition derived from80-99.95 vol. % of a petroleum fraction feedstock, and 20-0.05 vol. % ofa renewable fuel oil.

In certain embodiments, a method of processing a petroleum fraction witha substituted amount of a renewable fuel oil in the presence of acatalyst results in an increased or improved yield of transportationfuel for example, and increase of at least 0.5 wt. %, relative to theidentical process on an equivalent energy or carbon content basis of thefeedstream wherein the petroleum fraction is not substituted with therenewable fuel oil. For example, the improved or increasedtransportation fuel yield may be a gasoline, a diesel fuel, a LPG, aheating oil, a jet fuel, an LCO, a transportation fuel, and/or a powerfuel.

In certain embodiments, a method of improving or increasing petroleumconversion, relative to an equivalent energy input of a fraction of thepetroleum, in a refinery may comprise processing a lesser amount of thefraction of the petroleum with a renewable fuel oil in the presence of acatalyst. For example, the method of improving or increasing petroleumfraction feedstock conversion may comprise processing the petroleumfraction feedstock with a renewable fuel oil feedstock in the presenceof a catalyst. In certain embodiments, a method of improving orincreasing fuel yield from a petroleum feedstock, may compriseprocessing a fraction of the petroleum with a renewable fuel oil in thepresence of a catalyst. For example, the improved or increased fuelyield may be a gasoline, a diesel fuel, a LPG, a heating oil, a jetfuel, an LCO, a transportation fuel, or a power fuel.

In certain embodiments, a method of preparing a fuel may compriseprocessing a petroleum fraction feedstock with a renewable fuel oilfeedstock in the presence of a catalyst. For example, the method ofpreparing a fuel may comprise providing a renewable fuel oil feedstockfor processing with a petroleum fraction feedstock in the presence of acatalyst. In certain embodiments, the method of preparing a fuel maycomprises: i) processing a petroleum fraction feedstock with a renewablefuel oil feedstock in the presence of a catalyst; and ii) optionally,adjusting feed addition rates of the petroleum fraction feedstock, therenewable fuel oil feedstock, or both, to target a particular fuelproduct profile, riser temperature, or reaction zone temperature; oriii) optionally, adjusting catalyst to combined petroleum fractionfeedstock and renewable fuel oil feedstock ratio (catalyst:oil ratio) totarget a particular fuel product profile, riser temperature, or reactionzone temperature; wherein the catalyst:oil ratio may be a weight ratioor a volume ratio.

For example, the method of preparing a fuel may comprises: i) processinga petroleum fraction feedstock with a renewable fuel oil feedstock inthe presence of a catalyst; ii) adjusting feed addition rates of thepetroleum fraction feedstock, the renewable fuel oil feedstock, or both,to target a particular fuel product profile, riser temperature, orreaction zone temperature; and iii) optionally, adjusting catalyst tocombined petroleum fraction feedstock and renewable fuel oil feedstockratio (catalyst:oil ratio) to target a particular fuel product profile,riser temperature, or reaction zone temperature; wherein thecatalyst:oil ratio may be a weight ratio or a volume ratio. For example,the method of preparing a fuel may comprises: i) processing a petroleumfraction feedstock with a renewable fuel oil feedstock in the presenceof a catalyst; ii) optionally, adjusting feed addition rates of thepetroleum fraction feedstock, the renewable fuel oil feedstock, or both,to target a particular fuel product profile, riser temperature, orreaction zone temperature; and iii) adjusting catalyst to combinedpetroleum fraction feedstock and renewable fuel oil feedstock ratio(catalyst:oil ratio) to target a particular fuel product profile, risertemperature, or reaction zone temperature; wherein the catalyst:oilratio may be a weight ratio or a volume ratio. For example, the methodof preparing a fuel may comprises: i) processing a petroleum fractionfeedstock with a renewable fuel oil feedstock in the presence of acatalyst; ii) adjusting feed addition rates of the petroleum fractionfeedstock, the renewable fuel oil feedstock, or both, to target aparticular fuel product profile, riser temperature, or reaction zonetemperature; and iii) adjusting catalyst to combined petroleum fractionfeedstock and renewable fuel oil feedstock ratio (catalyst:oil ratio) totarget a particular fuel product profile, riser temperature, or reactionzone temperature; wherein the catalyst:oil ratio may be a weight ratioor a volume ratio. For example, the method may include increasing ordecreasing the wt. % or vol. % of the renewable fuel oil to favor aparticular fuel product profile, such as favoring an increased yield ofgasoline, diesel fuel, LPG, heating oil, jet fuel, or LCO, such asgasoline, LCO, or gasoline and LCO. For example, the method may includeincreasing or decreasing the catalyst:oil ratio to favor a particularfuel product profile, such as favoring an increased yield of gasoline,diesel fuel, LPG, heating oil, jet fuel, or LCO, such as gasoline, LCO,or gasoline and LCO. For example, the method of preparing a fuel producthaving at least 70 vol. % of gasoline and LCO may comprise the followingsteps: i) processing a petroleum fraction feedstock with a renewablefuel oil feedstock in the presence of a catalyst; and ii) optionally,adjusting feed addition rates of the petroleum fraction feedstock, therenewable fuel oil feedstock, or both, to target a particular fuelproduct profile, riser temperature, or reaction zone temperature; oriii) optionally, adjusting catalyst to combined petroleum fractionfeedstock and renewable fuel oil feedstock ratio (catalyst:oil ratio) totarget a particular fuel product profile, riser temperature, or reactionzone temperature; wherein the catalyst:oil ratio may be a weight ratioor a volume ratio. For example, the fuel prepared may be a gasoline, adiesel fuel, a LPG, a heating oil, a jet fuel, an LCO, a transportationfuel, or a power fuel.

In certain embodiments, the method includes processing or co-processinga petroleum fraction feedstock in the presence of a catalyst with arenewable fuel oil in a refinery to produce a fuel product, such as acellulosic renewable identification number-compliant fuel product. Forexample, the prepared fuel product from processing or co-processing apetroleum fraction feedstock with a renewable fuel oil in a refinery mayinclude a distillated fuel or distillate fuel oil, a heating oil,refined-heating oil, heating oil distillate, or a refined-heating oildistillate. In certain embodiments, the prepared fuel product mayinclude one or more of a transportation fuel, such as a high-valuetransportation liquid, a gasoline, a light cycle oil (LCO), a dieselfuel, a jet fuel, an LPG (C4-C3), a heating oil distillate, a middledistillate, a high-value middle distillate, a combustible fuel, a powerfuel, a generator fuel, a generator-compliant fuel, an internalcombustion engine-combustible fuel, a valuable fuel or valuable fuelcomponent, a cellulosic fuel, a cellulosic-renewable indexnumber-compliant fuel, or a D-code 1-7-compliant fuel, in accordancewith U.S. renewable fuel standard program (RFS) regulations (such as aD-code 1-compliant fuel, a D-code 2-compliant fuel, a D-code 3-compliantfuel, a D-code 4-compliant fuel, a D-code 5-compliant fuel, a D-code6-compliant fuel, or a D-code 7-compliant fuel). In certain embodiments,the prepared fuel product may have a product file of 50-55 vol. %gasoline, 15-20 vol. % LCO, 15-20 vol. % LPG, and 6-12 vol. % HCO. Forexample, the prepared fuel product may have a product file of 45-55 vol.% gasoline, 15-20 vol. % LCO, 15-20 vol. % LPG, and 6-12 vol. % HCO. Forexample, in certain embodiments, the prepared fuel product may beexclusive of a heavy cycle oil (LCO), dry gas, or coke. In certainembodiments, the prepared fuel product may be a diesel fuel, a gasoline,a jet fuel, a cellulosic fuel, a cellulosic-renewable indexnumber-compliant fuel, or a heating oil. For example, the prepared fuelproduct may be a cellulosic fuel, such as a diesel fuel, acellulosic-renewable index number qualifying-diesel fuel, a gasoline, acellulosic-renewable identification number qualifying-gasoline, aheating oil, cellulosic-renewable index number qualifying-heating oil, acellulosic fuel qualifying for cellulosic renewable identificationnumbers, or a D-code 7-compliant fuel.

In certain embodiments, the prepared fuel product may be produced via afuel pathway specified in U.S. renewable fuel standard program (RFS)regulations for generating cellulosic renewable identification numbers.For example, the pathway may include a transportation fuel pathway, adiesel fuel pathway, a gasoline pathway, a heating oil pathway, acellulosic fuel pathway, a cellulosic renewable identificationnumber-compliant pathway, a pathway compliant in generating, producing,preparing, or making, a cellulosic renewable identificationnumber-compliant fuel, or a pathway that complies with a fuel pathwayspecified in U.S. renewable fuel standard program (RFS) regulations forgenerating the cellulosic renewable identification number. For example,the prepared fuel product may be a fuel compliant with U.S. renewablefuel standard program (RFS) regulations for generating acellulosic-renewable index number, such as a cellulosic fuel compliantwith U.S. renewable fuel standard program (RFS) regulations forgenerating a cellulosic-renewable index number, or a co-processedrefinery product suitable for substantially generating a cellulosicrenewable identification number. In certain embodiments, the preparedfuel product may be prepared according to a method that may be compliantwith generating one or more, such as a plurality, ofcellulosic-renewable index numbers. For example, the processed fuelproduct may be capable of producing, generating a cellulosic renewableidentification number. In certain embodiments, the prepared fuel productmay be exchangeable, tradable, or sellable, for a obtaining one or morecellulosic renewable identification numbers. The prepared fuel product,and the method of preparing the same, may be capable of satisfyingrenewable volume obligations established by U.S. renewable fuel standardprogram (RFS) regulations. For example, the prepared fuel product may becompliant with meeting U.S. renewable volume obligations. In certainembodiments, the prepared fuel product may be produced via a methodcomprising obtaining one or more cellulosic-renewable identificationnumbers based on the amount of fuel produced complying with, or meeting,the definition of a cellulosic fuel. For example, the cellulosic fuelmay be a gasoline, a diesel, an LCO, an LPG, a jet fuel, or a heatingoil. In certain embodiments, the method may comprise trading, selling,or exchanging one or more cellulosic-renewable identification numbersobtained from the prepared fuel product, such as a cellulosic-renewableidentification number-compliant fuel having a D-code of 7, in accordancewith US regulations.

In certain embodiments, a pathway for preparing a cellulosic renewableidentification number-compliant fuel may comprise processing a petroleumfraction feedstock with a renewable fuel oil feedstock in the presenceof a catalyst. In certain embodiments, a method for meeting renewablevolume obligations (RVO) according to US RFS regulations may compriseprocessing a petroleum fraction feedstock with a renewable fuel oil(RFO) feedstock in the presence of a catalyst.

FIG. 4 illustrates a coking unit for use with the present system,according to one embodiment. A coker or coker unit may be a type ofconversion unit that may be used in an oil refinery processing unit thatconverts the conditioned renewable oil feedstock 101. The processthermally cracks the long chain hydrocarbon molecules in the residualoil feed into shorter chain molecules.

A coke may either be fuel grade (high in sulphur and metals) or anodegrade (low in sulphur and metals). The raw coke directly out of a cokermay be often referred to as green coke. In this context, “green” meansunprocessed. The further processing of green coke by calcining in arotary kiln removes residual volatile hydrocarbons from the coke. Acalcined petroleum coke may be further processed in an anode baking ovenin order to produce anode coke of the desired shape and physicalproperties. The anodes are mainly used in the aluminum and steelindustry.

Crude oil extracted from field operations, such as the Western Canadianoil sands, may be pre-processed before it may be fit for pipelinetransport and utilization in conventional refineries. Thispre-processing may be called ‘upgrading’ (performed by a field upgraderunit), the key components of which are as follows:

-   -   Removal of water, sand, physical waste, and lighter products;    -   Hydrotreating; and    -   Hydrogenation through carbon rejection or catalytic        hydrocracking (HCR).

As carbon rejection may be very inefficient and wasteful in most cases,catalytic hydrocracking may be preferred in some cases.

Hydrotreating and hydrocracking together may be known ashydroprocessing. The big challenge in hydroprocessing may be to dealwith the impurities found in heavy crude, as they poison the catalystsover time. Many efforts have been made to deal with this to ensure highactivity and long life of a catalyst. Catalyst materials and pore sizedistributions are key parameters that need to be optimized to handlethese challenges and this varies from place to place, depending on thekind of feedstock present.

Hydrocracking may be a catalytic cracking process assisted by thepresence of an elevated partial pressure of hydrogen gas. Similar to thehydrotreater, the function of hydrogen may be the purification of thehydrocarbon stream from sulfur and nitrogen hetero-atoms.

In certain embodiments, a renewable fuel oil may be introduced into thefield upgrading operations. Methods as previously described may beemployed to feed the renewable fuel into any of the unit operationsassociated with field upgrader systems.

In certain embodiments, a renewable fuel oil may be introduced into alube oil refinery facility. Specifically renewable fuel may beintroduced into the hydrotreater section of the refinery where gasolineand other transportation fuels are produced. Some renewable fuels suchas vegetable oil may have properties that enable the blending,substitution or improvement to the lube oil products.

In certain embodiments, a renewable fuel oil may be introduced into arefinery system, such as an FCC, a hydrotreating unit, or a hydrocrackerunit, in a range of between 0.05 wt. % and 20 wt. %, relative to theamount of a petroleum fraction feedstock introduced, such as between0.05 wt. % and 15 wt. %, between 0.05 wt. % and 14 wt. %, between 0.05wt. % and 13 wt. %, between 0.05 wt. % and 12 wt. %, between 0.05 wt. %and 11 wt. %, between 0.05 wt. % and 10 wt. %, between 0.05 wt. % and 9wt. %, between 0.05 wt. % and 8 wt. %, between 0.05 wt. % and 7 wt. %,between 0.5 wt. % and 20 wt. %, between 0.5 wt. % and 15 wt. %, between0.5 wt. % and 10 wt. %, between 1 wt. % and 15 wt. %, between 2 wt. %and 12 wt. %, between 3 wt. % and 10 wt. %, between 4 wt. % and 9 wt. %,or between 7 wt. % and 15 wt. %, relative to the amount of a petroleumfraction feedstock introduced.

In certain embodiments, a renewable fuel oil may be introduced into arefinery system, such as an FCC, a hydrotreating unit, or a hydrocrackerunit, in a range of between 0.05 wt. % and 20 wt. %, relative to thetotal amount of a petroleum fraction feedstock and the renewable fueloil introduced, such as between 0.05 wt. % and 15 wt. %, between 0.05wt. % and 14 wt. %, between 0.05 wt. % and 13 wt. %, between 0.05 wt. %and 12 wt. %, between 0.05 wt. % and 11 wt. %, between 0.05 wt. % and 10wt. %, between 0.05 wt. % and 9 wt. %, between 0.05 wt. % and 8 wt. %,between 0.05 wt. % and 7 wt. %, between 0.5 wt. % and 20 wt. %, between0.5 wt. % and 15 wt. %, between 0.5 wt. % and 10 wt. %, between 1 wt. %and 15 wt. %, between 2 wt. % and 12 wt. %, between 3 wt. % and 10 wt.%, between 4 wt. % and 9 wt. %, or between 7 wt. % and 15 wt. %,relative to the total amount of a petroleum fraction feedstock and therenewable fuel oil introduced.

In certain embodiments, a method of preparing a fuel product may includeprocessing 80-99.95 wt. % of a petroleum fraction feedstock with 20-0.05wt. % of a renewable fuel oil in the presence of a catalyst. Forexample, the method may include processing 80 wt. % of the petroleumfraction feedstock and 20 wt. % of the renewable fuel oil, such as 85wt. % petroleum fraction feedstock and 15 wt. % renewable fuel oil, 90wt. % petroleum fraction feedstock and 10 wt. % renewable fuel oil, 95wt. % petroleum fraction feedstock and 5 wt. % renewable fuel oil, 98wt. % petroleum fraction feedstock and 2 wt. % renewable fuel oil, or99.5 wt. % petroleum fraction feedstock and 0.5 wt. % renewable fueloil. In certain embodiments, a method of preparing a fuel product mayinclude processing a petroleum fraction feedstock and a renewable fueloil in a weight ratio in the range of between 80:20 to 99.95:0.05. Forexample, the method may include processing the petroleum fractionfeedstock and the renewable fuel oil in a 98:2 weight ratio, such as a95:5, 90:10, 85:15, or 80:20 weight ratio. In certain embodiments, amethod of preparing a fuel product may include processing 20-0.05 wt. %of a renewable fuel oil, relative to the amount of the petroleumfraction feedstock processed. In certain embodiments, a method ofpreparing a fuel product may include processing 20-0.05 wt. % of arenewable fuel oil, relative to the total amount of the petroleumfraction feedstock and the renewable fuel oil. In certain embodiments, amethod of preparing a fuel product may include processing 20-0.05 vol. %of the renewable fuel oil, relative to the volume of the petroleumfraction feedstock processed. In certain embodiments, a method ofpreparing a fuel product may include processing 20-0.05 vol. % of therenewable fuel oil, relative to the total volume of the petroleumfraction feedstock and the renewable fuel oil.

In certain embodiments, the weight ratio of the total amount ofpetroleum fraction feedstock and renewable fuel oil introduced into arefinery system to the amount of catalyst utilized, or the total amountof the combined petroleum fraction feedstock and renewable fuel oilintroduced into a refinery system that contacts the catalyst utilized inthe refinery system (sometimes referred to as a “catalyst-to-oil ratio”or “catalyst:oil ratio”) may be in the range of between 4:1 to 15:1. Forexample, the catalyst-to-oil ratio may be in the range of between 4:1 to13:1, such as between 5:1 to 10:1, between 5:1 to 9:1, between 6:1 to8:1, between 4:1 to 7:1, or between 6:1 to 7:1. For example, thecatalyst-to-oil ratio may be 4:1, such as 5:1, 6:1, 7:1, 8:1, 9:1, 10:1,11:1, 12:1, 13:1, 14:1, or 15:1.

In certain embodiments, prior to the introduction of the renewable fueloil (RFO) feedstock into a refinery for co-processing with a petroleumfraction feedstock, the renewable fuel oil (RFO) feedstock may beblended with vegetable-based oils, alcohols, or other cellulosic-derivedmaterials, as a means to condition the renewable fuel oil (RFO)feedstock prior to processing. In certain embodiments, the renewablefuel oil (RFO) feedstock may be blended with vegetable-based oils,alcohols, or other cellulosic-derived materials if the water content ofthe renewable fuel oil (RFO) feedstock may be less than 20 wt. %, suchas less than 15 wt. %, 10 wt. %, or less than 5 wt. %. For example, arenewable fuel oil (RFO) feedstock having a water content less than 20wt. % or less than 15 wt. %, may be blended with one or more alcohols,such as methanol, ethanol, propanol, isopropyl alcohol, glycerol, orbutanol, prior to introduction into the refinery.

According to one embodiment the blends of renewable oils with alcohols,or vegetable based oils can also be mixed or blended with petroleummaterials with or without a surfactant prior to injection into therefinery systems including the FCC.

According to one embodiment recycle products from the downstream, orother unit operation in the refinery can be a source of blend materialwith the renewable oil prior to injection into the refinery system orFCC.

According to one embodiment the renewable oil or renewable fuel may beemulsified with a petroleum fraction based fuel then introduced into therefinery process. The emulsification may be mechanically achieved orachieved through the use of an appropriate chemical emulsificationmedia.

According to one embodiment, the present system includes processing ofbiomass or renewable feedstock into any pyrolysis system. Exemplaryreactor systems for injecting the conditioned renewable feedstock intoinclude, but are not limited to, entrained down-flow, ablative reactors,transport bed, fluid bed, screw or auger systems, and rotating cone.Characteristics of a fast pyrolysis reactor for maximal oil productionare the very rapid heating of the conditioned renewable feedstock, andrapid quenching of the produced vapors. A more detailed discussion offast pyrolysis may be found in the Background section of this document.

FIG. 5 illustrates an exemplary upgraded feed injection system for usewith the present system, according to one embodiment. Feed nozzles thatare modified for the properties of conditioned renewable fuel feedstock101, and nozzles can be converted to stainless steel, or otherappropriate metallurgy, if they are not already and adjusted to injectrenewable oil to provide an upgrade to existing systems.

According to one embodiment, conditioned renewable fuel oil may beutilized in FCC units that presently utilize a catalyst known as ZSM-5.ZSM-5 may be shown to be a favorable catalyst for the conversion ofbiomass to hydrocarbons.

FIG. 6 illustrates an exemplary FCC unit with dual risers, according toone embodiment. A dual riser system may comprise a least one inputelement for introducing a petroleum fraction and at least one elementfor introducing a renewable fuel oil such that they can contact thecatalyst and be co-processed. Another embodiment may include a dualriser system that may be retro-fitted to provide at least one elementfor introducing a renewable fuel oil such that they can contact thecatalyst and be co-processed. Feedstock 101 including renewable fuel oilmay be fed into a second riser of a two riser FCC (as shown in FIG. 6).

Contact time of the catalyst with the feedstock may comprise theresidence time in the riser and the residence time in the risertermination system. For example, in some embodiments the riser residencetimes may be about 2 to 3 seconds with the residence time in terminationsystem may be an additional 1 to 2 seconds. This may lead to an overallcatalyst contact time of about 3 to 5 seconds. For example, thefeedstock may interact with the catalyst for greater than 2 second, forexample greater than 3 seconds, greater than 4 seconds such as 3 to 7seconds or 2 to 4 seconds or 3 to 5 seconds.

In another embodiment, a method and system for introducing renewablefuel or renewable fuel oil into a refinery FCC unit that may besimultaneously processing a petroleum fraction, with the contact time ofthe FCC catalyst being for a period of greater than 3 seconds, forexample 3 to 7 seconds or 3 to 5 seconds.

According to one embodiment, the addition rate RFO in a refinery FCCthat may be processing a petroleum fraction may be in an amount of lessthan 10% by weight, relative to the total weight of the petroleumfraction and RFO, (e.g., in a range between 0.05% by weight and 10% byweight) of a thermally produced renewable oil with the contact time ofthe FCC catalyst and renewable oil for a period of greater than 3seconds.

In certain embodiments FCC units may use steam to lift the catalyst aswell provide dilution media for residence time control. The lift steamcan enter the FCC reactor riser from the bottom of the unit and/orthrough nozzles on the side of the reactor. These nozzles may be locatedbelow, above or co-located with the feedstock (either the RFO feed, GOfeed or both RFO and GO feed) injection point.

In certain embodiments, it may be useful, because of the properties ofrenewable fuel oil, to employ a delivery system separate from thepetroleum feedstock feed port (or assembly) for introducing the RFOmaterial into an FCC unit. The separate delivery system may includetransfer from storage, preheat and deliver the renewable oil to anappropriate injection point on the FCC. To ensure contact between therenewable oil and the hydrocarbon feedstock the point of introductionmay be near to the petroleum feedstock injection nozzles which aretypically located in the lower third of the FCC riser.

According to one embodiment, renewable oil may be introduced into thelift steam line at proximate the bottom of the FCC reactor riser, forexample below the mid-point of the riser. In an alternative embodiment,the renewable oil may be introduced into the velocity steam line thatcould be located either upstream or downstream of the hydrocarboninjection point. According to a further embodiment, renewable oil may beintroduced through an atomizing nozzle that may be inserted into the oneor multiple steam lines or may be introduced into the recycle lift vaporline or lines.

According to one embodiment, the addition rate of renewable oil may becontrolled by a separate delivery system (i.e., separate from thehydrocarbon delivery system) into the lower third of the FCC reactorriser. According to an alternative embodiment, the addition rate ofrenewable oil may be controlled by a separate delivery system into oneor multiple lift steam lines. In a further embodiment, the addition rateof renewable oil may be controlled by a separate delivery system into anavailable port in the lower third of the FCC reactor riser. In anotheralternative embodiment, the addition rate of renewable oil may becontrolled by a separate delivery system and introduced into one of thehydrocarbon nozzles or injectors either separately or with hydrocarbon.

In certain embodiments, the method may comprise: producing a renewableoil based feedstock; introducing the renewable oil based feedstock intoa refinery system, wherein the refinery system conversion unit may beselected from a group consisting of a fluid catalytic cracker, a coker,a field upgrader system, a lube oil refinery facility, a hydrocracker,and a hydrotreating unit; and co-processing the renewable oil basedfeedstock with a petroleum fraction feedstock. For example, the methodmay comprise (i) producing the renewable oil based feedstock, whichcomprises rapid thermal conversion of biomass, and (ii) conditioning therenewable oil based feedstock to enable introduction into the refinerysystem. In such instances, the conditioning of the renewable oil basedfeedstock may comprise controlling an ash content to be in a range ofbetween 0.005 wt. % and 0.5 wt. %; controlling a pH to be in a range ofbetween 2.0 and 8.0, such as 2.0 and 6.0; and controlling a watercontent to be in a range between 0.05 wt. % and 30 wt. %. In certainembodiments, the petroleum fraction feedstock employed in the method maybe a VGO. In certain embodiments, the method may include injecting therenewable oil feedstock into a catalytic riser of a fluid catalyticcracking unit. For example, the renewable oil feedstock may be injectedupstream of a VGO inlet port of a fluid catalytic cracking unit, therenewable oil feedstock may be injected downstream of a VGO inlet portof a fluid catalytic cracking unit, the renewable oil feedstock may beinjected into a riser quench line of a fluid catalytic cracking unit, orthe renewable oil feedstock may be injected into a second riser of a tworiser fluid catalytic cracking unit. In certain embodiments, the systemmay comprise: a production facility for producing a renewable oil basedfeedstock; and a refinery system, wherein the refinery system may beselected from a conversion unit consisting of a fluid catalytic cracker,a coker, a field upgrader system, a lube oil refinery facility, ahydrocracker, and a hydrotreating unit, wherein the renewable oil basedfeedstock may be introduced into the refinery system, and the renewableoil based feedstock may be co-processed with a petroleum fractionfeedstock in the refinery system.

EXAMPLES

Testing has been conducted using different equipment, various petroleumbased feedstocks, and an FCC catalyst with various quantities of arenewable fuel liquid. The majority of the experiments involved theprocessing of a renewable fuel oil with a typical commercially-producedgas oil in an Advanced Cracking Evaluation (ACE) FCC unit. In addition,testing has been conducted in a fluid-bed Microactivity Test reactor(MAT) unit with a commercial equilibrium catalyst.

Example 1 Testing Equipment

The co-processing of petroleum fraction feedstock with varying amountsof renewable fuel oil (RFO) (or the processing of the petroleum fractionfeedstock alone as a comparator), were conducted in a Model R+ KayserTechnology Advanced Cracking Evaluation (ACE) FCC unit (herein referredto as “ACE testing unit” or “FCC unit”), using an FCC catalyst.

The ACE testing unit had hardware and software that enabled multipleruns to be accurately performed without operator intervention. Thereactor consisted of a 1.6 cm ID stainless steel tube with a taperedconical bottom. A diluent (nitrogen), flowing from the bottom, fluidizedthe catalyst and also served as the stripping gas at the end of acatalytic run. The feedstock that was introduced in to the ACE testingunit to be cracked was fed from the top via an injector tube with itsoutlet tip near the bottom of the fluid bed. An injector position ofapproximately 2.86 cm, measured from the bottom of the reactor, wasused.

The ACE testing unit used a cyclic operation of a single reactor(containing a batch of fluidized catalyst particles) to simulate each ofthe sections of a commercial FCC unit: (a) riser reactor—injection offeed over the catalyst; (b) catalyst stripper—catalyst stripping for aspecified duration; (c) regeneration—catalyst regeneration with air atelevated temperatures.

The reactor remained in the furnace during catalyst addition andwithdrawal. Each test run was performed under atmospheric pressureconditions, and a reactor temperature of 510° C. (950° F.). A constantload of 9 g of equilibrium catalyst and the Variable Time on Streammethod of varying feed injection time at a constant injection rate of1.2 g/min were used to obtain the desired catalyst-to-oil ratios. Thefluidized bed regeneration temperature was maintained at 712° C. (1313°F.).

Feedstock or Feedstock Combinations:

The renewable fuel oil (RFO) feedstock utilized in the Examples belowwas produced from rapid thermal processing of a wood residue feedstockin a commercial fast pyrolysis process, according to any one of U.S.Pat. No. 7,905,990, U.S. Pat. No. 5,961,786, and U.S. Pat. No.5,792,340, each of which is herein incorporated by reference in theirentirety. The properties of the renewable fuel oil (RFO) feedstock aresummarized in Table 1.

TABLE 1 Parameter Test Method RFO Water Content, wt. % ASTM E203 26.98%Viscosity @ 40° C., cSt ASTM D445 58.9 Viscosity @ 60° C., cSt AshContent, wt. % EN 055 0.02% Solids Content, wt. % ASTM D7579 0.04%Density @ 20° C., kg/dm³ EN 064 1.1987 pH ASTM E70-07 2.44 CarbonContent, wt. % as is ASTM D5291 41.80% Hydrogen Content, wt. % as isASTM D5291 7.75% Nitrogen Content, wt. % as is ASTM D5291 0.28% SulfurContent, wt. % as is ASTM D5453 0.01% Oxygen Content, wt. % as is ByDifference 50.14% HHV (as is), cal/g ASTM D240 4093.8 HHV (as is), MJ/kgASTM D240 17.1 HHV (as is), BTU/lb ASTM D240 7369

Separate, independent testings were conducted in an ACE testing unitthat processed, or co-processed, the following feedstock or feedstockcombinations (by feeding or co-feeding):

-   -   (1) 100 wt. % non-hydrotreated vacuum gas oil (VGO) feedstock,        as a petroleum fraction feedstock (herein referred to as “VGO        feedstock”);    -   (2) 98 wt. % VGO feedstock and 2 wt. % renewable fuel oil (RFO)        feedstock;    -   (3) 95 wt. % VGO feedstock and 5 wt. % renewable fuel oil (RFO)        feedstock; and    -   (4) 90 wt. % VGO feedstock and 10 wt. % renewable fuel oil (RFO)        feedstock.        Each of these feedstock or feedstock combinations were processed        or co-processed in the ACE testing unit at a constant cracking        temperature of 510° C. (950° F.).

Catalyst-to-Oil Ratios:

For each feedstock or feedstock combination, several runs wereconducted, independently employing different catalyst-to-oil ratios(“cat./oil ratios”): ranging from 4:1 to 11.25:1, specifically 4:1, 6:1,8:1, 10:1, and 11.25:1.

Analysis:

Each of the liquid samples that were formed from the processing orco-processing of the feedstock or feedstock combinations in the ACEtesting unit were collected and sent for analysis. Gas chromatographicanalysis was conducted on the dry gas product. Coke content wasdetermined by analyzing for the quantity of carbon dioxide produced fromthe regeneration step of the testing procedure. The ACE testing resultsfor each run included conversion and yields of dry gas, liquefiedpetroleum gas (LPG, the C₃-C₄), gasoline (C₅-221° C.), light cycle oil(LCO, 221-343° C.), heavy cycle oil (HCO, 343° C.+), and coke. Theconversion of the feedstock or feedstock combination was determined bycalculating the difference between the amount of feedstock or feedstockcombination and the amount of unconverted material defined as liquidproduct boiling above 221° C.

It may be known that the quality of the feedstock charged into an FCCunit can be the single greatest factor affecting product yields andquality. In the ACE tests, the same VGO feedstock material was usedthroughout the study. Therefore, the results disclosed herein can beused in relative terms, but may not necessarily represent absoluteyields that would be achieved using other alternative FCC feedstocks.The results disclosed herein are, however, very indicative, particularlyin showing yield and conversion trends relative to the VGO control testdata.

Normalization or Equivalence of Feedstock and Feedstock Combinations:

The conversion and yield curves, expressed on an equivalent energy inputor equivalent carbon input basis, demonstrate an unexpected effectresulting from the combination varying amounts of the renewable fuel oil(RFO) feedstock with the VGO feedstock in a FCC-type unit (the ACEtesting unit). The renewable fuel oil (RFO) feedstock has about one halfof the carbon and energy content of the VGO feedstock (for an equivalentmass). For example, when comparing the results from the feedstockcombination of 98 wt. % VGO feedstock and 2 wt. % renewable fuel oil(RFO) feedstock against those of the 100 wt. % VGO feedstock, 2 wt. % ofthe renewable fuel oil (RFO) feedstock may be substituted in place of 2wt. % of VGO feedstock, which means approximately 1% less carbon and 1%less energy are available in the FCC unit for subsequent conversion tothe desired products. If the renewable fuel oil (RFO) feedstock carbonand energy were converted to gasoline in the same proportions as the VGOfeedstock carbon and energy, then one would expect the gasoline yield todrop by 1%, in the case of the 2 wt. % renewable fuel oil (RFO)feedstock combination and when equal amounts of total mass or volume arefed into the FCC unit. However, the gasoline yield dropped by less than1% in this case, a phenomenon that was observed for all substitutionlevels (i.e., the 2 wt. %, 5 wt. %, and the 10 wt. % renewable fuel oil(RFO) feedstock combinations). Therefore, if the input may be expressedon an equivalent amount of carbon or energy into the FCC unit (i.e.,keeping the carbon input or energy input constant regardless of whetherneat VGO feedstock or combinations of VGO feedstock with renewable fueloil (RFO) feedstock (blends) are fed), there may be a measurableincrease in gasoline yield when renewable fuel oil (RFO) feedstock maybe combined or blended in with the VGO feedstock. It may be important tonote that when yields are expressed on a constant carbon or energy inputinto the FCC unit, implicit in this assumption may be that the totalmass or volume input into the FCC would increase with the substitutionof the renewable fuel oil (RFO) feedstock. In the case of the 2 wt. %renewable fuel oil (RFO) feedstock combination (blend), about 1%additional mass input to the FCC unit would be required to achieve thesame carbon or energy input as 100% VGO feed. In terms of volumeaddition, when accounting for the density differences between VGO andRFO, less than 1% additional volume of a 2 wt. % renewable fuel oil(RFO) feedstock combination (blend) to the FCC unit would result toachieve the same carbon or energy input into the FCC unit as neat VGOfeedstock.

The conversion and yield curves disclosed herein were generated usingthe mass yield experimental data that was generated from the ACE testingunit, coupled with the energy and carbon contents of the inputfeedstocks. In the case of energy-equivalent input basis, the massyields were divided by the feedstock energy input, which may be afunction of the proportion of the renewable fuel oil (RFO) feedstockaddition, using barrel of oil equivalent (BOE) as the energy units(i.e., 5.8 million BTU). The gasoline yield may be presented both on thebasis of energy input equivalence and carbon input equivalence. Carbonequivalence may be effectively the same as an energy-input basis, andmay be calculated from the generated mass data in a similar manner, butmay be generally a more clear and understandable expression thanequivalent energy basis.

The Figures discussed in this section highlight the conversion of neatVGO feedstock and renewable fuel oil (RFO) feedstock combinations orblends (2 wt. %, 5 wt. %, and 10 wt. %), as well as the respectiveyields of gasoline, LPG, dry gas, light cycle oil (LCO), heavy cycle oil(HCO) and coke, as a function of the Catalyst-to-Oil ratio (cat./oilratio) in the ACE testing unit. The effects of combining or blending thevarying amounts of the renewable fuel oil (RFO) feedstock with the VGOfeedstock on the gasoline octane numbers (both research-grade octane andmotor-grade octane numbers) are also disclosed herein.

Effect of RFO Blends on Conversion.

For the purposes of this example, the feedstock conversion, shown inFIGS. 7 and 8, is the input mass of VGO or RFO/VGO blend minus the massyields of both Light Cycle Oil (LCO) and Heavy Cycle Oil (HCO). ACEconversion data was generated with the FCC reaction temperature, thecatalyst weight, and the catalyst contact time all fixed for a given VGOor RFO blend feedstock, and the only variable was the catalyst:oilratio.

FIG. 7 illustrates the general increase in conversion of all of thefeeds at greater catalyst:oil ratios, on a mass basis. For the purposesof this example, in all cases, with the addition of RFO to the VGOfeedstock, there was a shift in the curves resulting in an increase massconversion. In other words, less LCO and HCO are produced as the amountof RFO in the VGO blend may be increased. At a catalyst:oil ratio of 8:1there may be an increase of conversion relative to the VGO conversionfrom approximately 0.7 to 1.4% as the RFO blend in VGO goes from 2 to 10wt. %. As indicated previously, since the energy content of the RFO maybe about half that of the VGO another way to represent the conversionmay be on energy input equivalency basis. In FIG. 8 the conversion ofthe VGO/RFO feedstock was found to dramatically increase as thesubstitution rate of RFO was increased.

Effect of RFO Blends on Gasoline Yields.

The primary purpose of FCC operations may be to produce optimal gasolineyields, and for the purposes of this study, the gasoline fraction may bedefined as the C₅-221° C. boiling point. FIG. 9 depicts the gasolineyield as a function of catalyst:oil ratio for the various feeds. Theyields of gasoline were found to initially increase as the catalyst:oilratio increased, up to a maximum at a catalyst:oil ratio of about 7:1 to8:1. Further increases in the catalyst:oil ratio resulted in a decreasein gasoline yield which may be attributed to overcracking under the setreactor conditions.

With respect to the gasoline yield for the various blends of RFO in thisstudy, there was a significant increase in net gasoline production whenan equivalent amount of VGO and RFO/VGO, in terms of input energy, maybe processed in the FCC. In general, as the blend of RFO in the VGO feedmay be increased, from 2 wt. % to 10 wt. %, there may be a measurableand consistent increase in gasoline yield. In addition, for thisexample, it appears that the maximum gasoline yield occurs at a slightlylower catalyst:oil ratio (at approximately 7:1) as compared to thereference VGO feed (approximately 8:1).

The gasoline yield can also be represented in terms of the amount ofcarbon in the feedstock that may be converted to gasoline. Similar tothe energy content basis, RFO has a lower carbon content than VGO.Therefore, in this example, less carbon may be delivered to the FCC unit(and less carbon may be made available for conversion to gasoline) asthe RFO proportion may be increased. The synergistic effect of RFOco-processing can be readily illustrated if the gasoline yields arebased on the amount of input carbon that may be converted to gasoline.

More specifically, as was the case with energy content, in thisexperiment the RFO has approximately one half of the carbon content ofVGO. The reference VGO has a carbon content of approximately 87 wt. %,while the carbon contents of the 2 wt. %, 5 wt. % and 10 wt. % RFOblends are 86.1%, 84.7% and 82.5%, respectively. The gasoline yields,expressed on an equivalent carbon input basis, are presented in FIG. 10as a function of catalyst:oil ratio in the ACE testing unit. In thisexample, there may be a significant and consistent increase in thegasoline yield as the substitution of RFO may be increased from 2 wt. %to 10 wt. %. These yields suggest that more carbon in the VGO may begoing to gasoline production then would otherwise be the case, withoutthe addition of the RFO in the blend. RFO may be synergisticallyaffecting either the cracking chemistry or catalyst activity in favor ofthe gasoline product.

Effect of RFO Blends on Liquid Petroleum Gas (LPG) Yield.

In FCC operation, LPG (defined as C₃+C₄ hydrocarbons) may be considereda valuable product since it consists of components that can be used asalkylation and petrochemical feedstocks. In this example, an increase inthe RFO blends in VGO results in an increase in LPG yields (on aconstant input energy basis), and this effect shown in FIG. 11. Thistrend also holds on the basis of constant carbon input to the FCC,suggesting that RFO addition preferentially causes higher carbonconversion to LPG.

Effect of RFO Blends on Dry Gas Yield.

In this example, the dry gas may be defined as the total of H₂, H₂S,carbon oxides, and C₁-C₂ hydrocarbons. Good operation of the FCC maykeep these products to a minimum as excessive dry gas production maycause downstream plant operation limitations with respect to gascompression. The effects on dry gas yields are shown in FIG. 12 and, asexpected, the dry gas yield increases as the catalyst:oil ratioincreases. On an equivalent energy input basis (i.e., the RFO/VGO blendtest having a similar energy input as the reference VGO energy input),there was an increase in dry gas make as the addition rate of RFOincreased. In this example, the predominant dry gas components for allcases were ethylene, methane and ethane.

Effect of RFO Blends on Light Cycle Oil (LCO) Yield.

In this example, the Light Cycle Oil (LCO) may be defined as thoseliquids that boil between 221-343° C., and the value of this product maybe dependent on the location and purpose of the refinery. Typically, inNorth America LCO may be not considered to be as desirable. However,where and when gasoline may be not in high demand, the FCC unit may beused as a source of middle distillate LCO that can be upgraded to dieseland No. 2 fuel oil. In this example, the effect of RFO blends on theproduction of LCO on an equivalent input energy basis (FIG. 13) wasfound to be relatively neutral at a level of 2 wt. % RFO addition, whileat 5 wt. % and 10 wt. % RFO addition, there was a measurable increase inthe production of LCO, expressed on an equivalent energy input (orcarbon input) basis.

Effect of RFO Blends on Heavy Cycle Oil (HCO) Yields.

In this example, the Heavy Cycle Oil (HCO) may be defined as thoseliquids that distil between 343° C. and 525° C. This material may begenerally considered by refineries to be relatively undesirable; anunconverted product with comparatively high aromatics and potentiallyhigh sulfur content. If possible, HCO production from VGO in an FCC unitshould be minimized. In this example, as FIG. 14 shows, the HCOproduction rate may be not significantly affected by the addition of 2wt. % or 5 wt. % RFO (by mass) in the VGO feedstock, while at 10 wt. %RFO substitution, an increase in the production of HCO may be clearlyapparent, on an equivalent energy input basis.

Effect of RFO Blends on Coke Yields.

In FCC operation, coke may be generally utilized to supply the necessaryprocess heat to drive the reactions. However, an increasing amount ofcoke production may eventually upset the heat balance of the FCC unit,resulting in higher temperatures in the catalyst regenerator. The effectof RFO blends on coke production in this example may be shown in FIG.15.

FIG. 15 illustrates that coke yield in this example may be notdramatically effected at the lower blends of RFO (i.e., 2 wt. % and 5wt. % by mass), while the blend of 10 wt. % RFO results in a measurableincrease in the coke production.

Effect of RFO Blends on Gasoline Yields on a 10,000 bbl/day Input Basis.

The primary purpose of FCC operations may be to typically produceoptimal gasoline yields, and for the purposes of this study, thegasoline fraction may be defined as the C₅-221° C. boiling point. FIG.16 depicts the gasoline yield as a function of catalyst:oil ratio forthe various feeds using a consistent 10,000 bbl/day input of the variousfeedstock blends on an RFO water free basis. Despite the fact that theamount of energy and carbon in the 10,000 bbl/day feed input of theRFO/VGO blends was less than the reference VGO, the yields of gasolinein this example were found to be unexpectedly higher than the referenceVGO feedstock case. In particular, in this example there was a dramaticimprovement in gasoline yield at the higher levels of RFO substitution.

Estimate of the Gallons of Gasoline Produced Per Ton of RFO.

Using the gallons of gasoline produced per ton of the reference VGO andcomparing to the gallons of gasoline produced per ton of RFO/VGO blendan estimate of the contribution of gallons of gasoline produced per tonof RFO was made. FIG. 17 illustrates the gallons of gasoline per ton ofRFO as a function of the level of RFO substitution. In this example, asthe level of substitution went from 2 wt. % to 10 wt. % the gallons ofgasoline produced per ton of RFO increased. Translating back to theoriginal biomass the yield of gasoline per ton of biomass was in excessof 90 gals/ton of biomass at the higher RFO levels of substitution.

Volume of Feed Input for an Energy Equivalent RFO/VGO Blend.

Refineries typically operate on a volume basis when handling,transferring, feeding and processing petroleum liquids. Accordingly, tomake a fair and equitable comparison when studying the effect of RFOaddition to VGO on gasoline yields, it may be important to measure theyields on either an energy-equivalent or carbon-equivalent input basis(i.e., what are the respective gasoline yields from VGO and RFO blendsfrom the identical amounts of input carbon or input energy). Inaddition, since the RFO in this example contains roughly half the carbonand energy content of VGO, in this example a small amount of additionaltotal feedstock volume had to be delivered to the FCC, as RFO may beblended into the VGO, in order to maintain an equivalent amount of inputcarbon or energy.

In regards to how much additional volume of RFO/VGO blends, in thisexample, had to be added to maintain constant carbon or energy input tothe FCC unit, is illustrated in FIG. 18. In this example, a surprisinglysmall amount of additional volume of RFO/VGO blend was only needed to beadded to compensate. This volume may be minimal, in this example, as theRFO may be much denser than VGO, so additional mass of VGO may be addedwith a proportionately less impact on total volume increase.

FIG. 18 indicates that, in this example, a 2 wt. % blend of RFO in VGOonly required a 0.8% increase in volume to deliver the same energy orcarbon to the FCC as neat (100%) VGO. In other words, for every 100barrels of neat VGO, 100.8 barrels of 2 wt. % RFO blend would berequired to deliver equivalent amounts of energy or carbon to the FCCunit. What is unexpected in this example, is that the gasoline yieldincreases much more than 0.8% over the typical range of FCC operatingconditions that were tested in the ACE testing unit.

In this example, the 5 wt. % RFO blend in VGO, an addition of only 2%volume would preserve the same energy or carbon input as neat VGO. Forevery 100 barrels of neat VGO, 102 barrels of 5 wt. % RFO blend would bedelivered to the FCC in order to maintain equivalent energy or carboninput. Once again, the gasoline yield is much greater than 2% over therange of ACE tests.

Example 2

Testing Equipment: The co-processing of renewable fuel oil (RFO) withpetroleum fraction feedstock (or the processing of the petroleumfraction feedstock alone as a comparator), was conducted in a fluid-bedMicroactivity Test reactor (MAT) unit (herein referred to as “MATtesting unit”), using a commercially available equilibrium catalyst.

A biomass-derived liquid having properties similar to that shown inTable 1 was obtained from a commercial rapid thermal conversion plantwhere residual wood was thermally cracked at mild temperature in a shortduration (typically less than 5 seconds) with about 70 to 80 wt. %liquid yield. A heavy gas oil (HGO) and a 5 wt. % RFO blend were crackedin a MAT testing unit at 510° C. (950° F.) with a constant oil injectiontime of 30 s using similar equilibrium catalyst as the case of Example1.

In this example, dry gas is composed of H₂, H₂S, CO, CO₂, and C₁-C₂hydrocarbons. The dry gas yield increased exponentially with conversion.At a given conversion in this example, the two feeds gave almostidentical dry gas yields. Only CO₂ but not CO was detected duringcracking of the two feeds with 0.02-0.08 wt. % CO₂ yield higher for theblend at 65-75 wt. % conversion indicating the decomposition orcombustion of the oxygenates in the blend. However, the blend producedless H₂ by 0.06 wt. % throughout the entire conversion in this studypossibly due to water formation.

Generally, gasoline (C₅-221° C. boiling point) is the major and the mostdesirable product in FCC operation. In this example, it was found thatat a given conversion, the blend lowered the gasoline yield by less than1 wt. % until the conversion was higher than 70 wt. %. Note that theblend itself contained 1.33 (calculated from RFO analysis) to 1.90 wt. %(Table 1) H₂O which could partially explain the drop in gasoline.Overcracking was observed for this particular blend at 75-80 wt. %conversion.

The gasoline yield may also be expressed in terms of volumetric flow perhour (FIG. 19). In this example, unexpectedly, the yield of gasoline wasshown to be greater for the RFO/HFO blend as compared to the yield ofgasoline from the processing of the reference HFO over a catalyst:oilratio of 4 to 9:1 (i.e., the usual operating range for a FCC unit).

Coke.

In FCC operation, coke is generally necessary to supply heat for feedpreheating and cracking. However, too much coke can seriously poison thecatalyst and overload the air blower during catalyst regeneration,causing excessively high temperatures in the regenerator. During thetesting it was found that, similar to the dry gas, both feeds gavealmost identical coke yield at a given conversion although the blend had0.27 wt. % higher Conradson Carbon Residue.

Oxygen.

For the purposes of this example, the oxygen distribution in the gaseousand liquid products also is of note. For instance, after cracking, mostof the oxygen in the blend in this example appeared as H₂O (74.6-94.1wt. %), with the rest forming CO₂ (0.7-5.3 wt. %). The liquid productswere analyzed for oxygen content and found to be below the detectionlimit (0.25 wt. %).

For the purposes of this example, it was generally observed that: (1)catalytic cracking of the blend containing 5 wt. % RFO resulted in theformation of water and carbon dioxide; (2) at a given severity andcompared with the base oil, the blend gave 1-3 wt. % higher conversionwhich increased with catalyst:oil ratio; (3) at a given conversion, theblend gave lower yields of LPG and gasoline than the base oil, whileother yields, including those of dry gas, light cycle oil (diesel),heavy cycle oil (heavy fuel oil), and coke, were almost the same for thetwo feeds, but among the dry gas components, higher CO₂ but lower H₂yields were observed for the blend; (4) an examination of the gasolineyield in terms of refinery flows (i.e., volumetric yield based on a setvolume of feed—example 10,000 bbl/day) indicated that the yield ofgasoline was greater for the RFO blend than the reference HFO over lowercatalyst:oil ratios, and that on a water-free RFO basis the yields ofgasoline and other valuable components were found to be greater than thereference HFO; (5) after cracking, most of the oxygen in the blendappeared as H₂O with the rest in the form of CO₂, and that the liquidproducts were analyzed for oxygen content and found to be below thedetection limit; and (6) when yields of an RFO blend and HGO arecompared on the basis of equivalent energy input to the MAT system,gasoline and LPG yields from the RFO blend are higher than correspondingyields from 100% HGO.

Example 3

A series of samples of a vacuum gas oil (VGO) and a 5 wt. % renewablefuel oil (RFO) blend were cracked in the MAT testing unit (reactor bed,Fluid-2) under similar conditions as in Example 2. The VGO employed inTable 2, labeled FHR CAT Feed, had a density of 0.9196 g/mL at 15.6° C.The RFO itself had a density of 1.198 g/mL, and a water content of 26.58(wt. %). The 5 wt. % RFO in VGO blend employed in Table 3, labeled 5 wt% RFO in FHR CF, had a density of 0.9243 g/mL at 15.6° C. In 100 lbs ofthe 5 wt. % RFO in VGO blend employed the water content was about 1.329lbs. The analysis, characterization, and results for the VGO samples arepresented in Tables 2, 3 (on an as fed basis), and Table 4 (refineryflows summary), while the analysis, characterization, and results forthe 5 wt. % RFO in VGO blend are presented in Tables 5, 6 (on an as fedbasis), Table 7 (on a water-free feed basis), Table 8 (refinery flowssummary) and Table 9 is a calculation of gallons of gasoline attributedto the input of RFO.

TABLE 2 Run Number C-1 C-2 C-3 C-4 C-5 C-6 Feed FHR CAT Feed CatalystGrace EC-2007 Coke Determination In situ In situ In situ In situ In situIn situ Catalyst contact time (sec) 30 30 30 30 30 30 Catalyst Charge(g) 8.9321 8.9321 8.9321 8.9321 8.9321 8.9321 Feed Charge (g) 1.84711.5069 1.0551 0.9328 0.7410 0.7292 Catalyst/Oil ratio (g/g) 4.836 5.9278.466 9.576 12.054 12.249 WHSV (g/h/g) 24.82 20.24 14.17 12.53 9.96 9.80Liquid yield (incl. H2O) 73.29 73.14 64.01 62.01 60.00 58.76 (wt. %)IBP/221° C. per Sim Dist 45.3667 49.8000 54.5676 57.7297 58.6757 58.4865(wt. %) IBP/343° C. per Sim Dist 76.0000 79.8889 83.6486 85.9737 86.192386.2121 (wt. %) Normalized Mass Balance (wt. % of feed) H2 0.14 0.160.22 0.24 0.24 0.26 H2S 0.00 0.00 0.00 0.00 0.00 0.00 CO 0.00 0.00 0.000.00 0.00 0.00 CO2 0.15 0.15 0.28 0.30 0.33 0.39 C1 0.33 0.36 0.58 0.740.66 0.77 C2 0.23 0.25 0.38 0.45 0.40 0.46 C2= 0.35 0.40 0.57 0.58 0.660.65 Total Dry Gas 1.20 1.33 2.04 2.31 2.28 2.53 C3 0.75 0.63 0.92 1.060.99 1.48 C3= 2.69 2.90 3.72 3.69 4.02 3.91 i-C4 3.11 3.34 4.16 4.264.76 4.62 n-C4 0.68 0.73 0.96 1.01 1.04 1.09 i-C4= 0.78 0.86 1.06 1.011.01 1.04 n-C4= 2.65 2.87 3.53 3.37 3.48 3.34 Total LPG 10.65 11.3314.34 14.41 15.31 15.48 Gasoline (C5-221° C.) 44.00 46.41 48.72 50.3650.94 50.69 LCO (221°-343° C.) 22.94 22.19 18.91 17.70 16.65 16.44 HCO(343° C.+) 18.47 15.49 11.46 9.69 9.35 9.23 Coke 2.74 3.26 4.54 5.535.47 5.63 H2O 0.00 0.00 0.00 0.00 0.00 0.00 Total 100.0 100.0 100.0100.0 100.0 100.0 Conversion 58.59 62.33 69.64 72.61 73.99 74.32

TABLE 3 Run Number C-1 C-2 C-3 C-4 C-5 C-6 Hydrocarbon Types in 200° C.-Gasoline (by New PIONA), wt. % Total s-Naphthenes 13.73 13.17 11.4910.50 7.26 9.53 Total s-i-Paraffins 23.06 22.20 18.28 16.59 20.61 15.06Total s-n-Paraffins 5.07 4.96 3.98 3.93 3.35 3.46 Total us-Naphthenes6.69 6.69 5.84 5.60 4.60 4.72 Total us-i-Paraffins 8.43 8.72 8.00 7.487.16 6.72 Total us-n-Paraffins 2.29 2.44 2.32 2.10 1.85 1.72 TotalAromatics 40.72 41.81 50.09 53.80 55.16 58.78 Total compounds 100.00100.00 100.00 100.00 100.00 100.00 Gasoline Specific Gravity 0.78370.7837 0.7930 0.7920 0.7956 0.8071 Research Octane No. (RON) 92.14 92.6496.09 97.12 94.43 96.12 Motor Octane No. (MON) 83.57 83.59 85.14 85.1480.03 84.19 Benzene (C6-Aromatics) 1.07 1.15 1.40 1.42 1.45 1.26 Toluene(C7-Aromatics) 4.92 5.23 6.84 6.77 7.25 7.52 Xylenes + Ethylbenzene (C8-12.33 12.89 16.36 16.11 18.97 19.98 Aromatics) C9-Aromatics 20.42 20.8523.95 23.58 26.31 28.57 C10-Aromatics 1.98 1.69 1.54 1.43 1.18 1.45 TLPOrganic Sulfur (mg/L) 1236 1262 1331 1369 1386 1391 Sulfur Distributionby bp (mg/L) Gasoline 23.1 23.80 26.10 37.80 48.50 38.60 LCO 483.7518.90 611.60 643.80 672.20 670.90 HCO 729.3 719.40 693.60 687.10 665.30681.70 TLP Nitrogen (wppm) 507 480 439 357 387 Nitrogen Distribution bybp (wppm) Gasoline 35.0 43.4 49.5 55.2 40.7 LCO 163.9 168.8 175.2 142.1165.1 HCO 308.5 267.8 214.0 159.9 180.6

TABLE 4 Run Number C-1 C-2 C-3 C-4 C-5 C-6 Dry Gas (lbs/hr) 1415.01579.5 2357.9 2702.1 2623.1 2872.5 C3 (bbls/hr) 5.7 4.8 6.9 8.0 7.5 11.2C3 = (bbls/hr) 19.7 21.3 27.3 27.1 29.6 28.7 C4 (bbls/hr) 25.5 27.3 34.435.5 39.0 38.4 C4 = (bbls/hr) 21.7 23.6 29.1 27.8 28.5 27.7 C5-429 F Cut(bbls/hr) 215.2 226.9 235.5 243.7 245.4 240.7 429-650 F Cut (bbls/hr)91.7 88.7 75.6 70.7 66.6 65.7 650 F Cut (bbls/hr) 64.8 54.3 40.2 34.032.8 32.4 Coke (lbs/hr) 3679.6 4376.5 6097.4 7429.4 7340.2 7551.3 CO(lbs/hr) 0 0 0 0 0 0 CO2 (lbs/hr) 198.0 206.0 375.2 401.2 436.7 528.5H2O (lbs/hr) 0 0 0 0 0 0 Dry Gas + CO + CO2 (lbs/hr) 1613.0 1785.62733.0 3103.3 3059.8 3401.0 Value/Cost 1.022 1.046 1.055 1.059 1.0601.045

TABLE 5 Run Number E-1 E-2 E-3 E-4 E-5 E-6 E-7 Feed 5 wt % RFO in FHR CFCatalyst Grace EC-2007 Coke Determination In situ In situ In situ Insitu In situ In situ In situ Catalyst contact time 30 30 30 30 30 30 30(sec) Catalyst Charge (g) 8.9321 8.9321 8.9321 8.9321 8.9321 8.93218.9321 Feed Charge (g) 2.0647 1.4407 1.1440 0.9075 0.8035 0.7163 0.6899Catalyst/Oil ratio (g/g) 4.326 6.200 7.808 9.843 11.116 12.470 12.947WHSV (g/h/g) 27.74 19.36 15.37 12.19 10.79 9.62 9.27 Liquid yield (incl.73.49 67.17 66.36 60.77 59.56 59.33 60.43 H2O) (wt %) IBP/221° C. perSim 46.0370 50.7273 54.7000 57.2333 57.0741 59.8649 59.5294 Dist (wt %)IBP/343° C. per Sim 77.1481 81.2593 83.5676 86.0769 85.7838 87.516186.5676 Dist (wt %) Normalized Mass Balance (wt. % of feed) H2 0.09 0.130.15 0.17 0.19 0.25 0.21 H2S 0.00 0.00 0.00 0.00 0.00 0.00 0.00 CO 0.000.00 0.00 0.00 0.00 0.00 0.00 CO2 0.29 0.24 0.29 0.41 0.46 0.42 0.45 C10.29 0.41 0.48 0.60 0.80 0.92 0.81 C2 0.23 0.31 0.34 0.41 0.50 0.55 0.49C2= 0.39 0.53 0.59 0.66 0.71 0.68 0.74 Total Dry Gas 1.29 1.61 1.84 2.262.66 2.82 2.69 C3 0.64 0.73 0.81 1.00 1.49 1.76 1,53 C3= 2.58 3.27 3.503.76 3.73 3.79 3.87 i-C4 2.87 3.72 3.89 4.35 4.23 4.64 4.68 n-C4 0.630.83 0.86 1.01 1.05 1.16 1.12 i-C4= 0.75 0.93 0.94 1.01 1.00 0.99 1.00n-C4= 2.54 3.21 3.17 3.32 3.31 3.33 3.26 Total LPG 10.01 12.69 13.1814.45 14.81 15.67 15.47 Gasoline (C5-221° C.) 43.97 46.61 48.56 49.4848.76 49.05 48.64 LCO (221°-343° C.) 22.89 20.40 18.88 17.07 16.61 15.9415.92 HCO (343° C+) 17.17 12.93 11.32 9.42 9.10 8.28 8.94 Coke 3.00 3.934.30 5.30 6.00 6.12 6.25 H2O 1.67 1.84 1.92 2.03 2.07 2.11 2.09 Total100.0 100.0 100.0 100.0 100.0 100.0 100.0 Conversion 59.94 66.67 69.8073.51 74.30 75.78 75.14

TABLE 6 Run Number E-1 E-2 E-3 E-4 E-5 E-6 E-7 Hydrocarbon Types in 200°C.-Gasoline (by New PIONA), wt. % Total s-Naphthenes 13.45 12.57 11.5211.06 7.38 6.67 9.64 Total s-i-Paraffins 22.44 19.31 17.53 17.15 18.8417.71 16.41 Total s-n-Paraffins 5.11 4.54 4.14 3.74 3.45 3.28 3.37 Totalus-Naphthenes 6.86 6.23 5.92 5.34 5.17 4.02 4.63 Total us-i-Paraffins9.09 8.16 8.00 7.10 6.79 7.09 7.71 Total us-n-Paraffins 2.40 2.24 2.471.95 2.00 1.57 2.14 Total Aromatics 40.65 46.95 50.41 53.66 56.37 59.6756.12 Total compounds 100.00 100.00 100.00 100.00 100.00 100.00 100.00Gasoline Specific Gravity 0.7828 0.7917 0.7834 0.7996 0.8011 0.80690.7992 Research Octane No. (RON) 92.09 93.31 94.84 96.50 93.54 94.7199.93 Motor Octane No. (MON) 83.33 84.34 84.51 85.18 80.64 81.03 86.37Benzene (C6-Aromatics) 1.12 1.15 1.32 1.39 1.47 1.34 1.55 Toluene(C7-Aromatics) 4.93 5.84 6.03 7.22 7.72 7.83 7.99 Xylenes + Ethylbenzene(C8- 12.21 14.70 14.89 18.25 18.70 20.29 19.12 Aromatics) C9-Aromatics20.48 23.44 22.56 25.52 26.60 28.41 25.97 C10-Aromatics 1.91 1.83 1.621.28 1.88 1.79 1.48 TLP Organic Sulfur (mg/L) 1204 1229 1228 1335 1323Sulfur Distribution by bp (mg/L) Gasoline 23.1 33.80 33.90 37.10 36.50LCO 469.2 510.20 549.40 657.10 651.30 HCO 711.7 685.40 644.70 640.80634.80 TLP Nitrogen (wppm) 525 502 451 407 381 378 410 NitrogenDistribution by bp (wppm) Gasoline 35.7 57.2 33.1 30.4 51.8 46.2 33.4LCO 169.7 175.6 161.7 168.4 152.8 161.4 175.8 HCO 319.8 269.5 256.0208.5 176.8 170.4 200.5

TABLE 7 Run Number E-1 E-2 E-3 E-4 E-5 E-6 E-7 Feed 5 wt % RFO in FHR CFCatalyst Grace EC-2007 Coke Determination In situ In situ In situ Insitu In situ In situ In situ Catalyst contact time 30 30 30 30 30 30 30(sec) Catalyst Charge (g) 8.9321 8.9321 8.9321 8.9321 8.9321 8.93218.9321 Feed Charge (g) 2.0647 1.4407 1.1440 0.9075 0.8035 0.7163 0.6899Catalyst/Oil ratio (g/g) 4.326 6.200 7.808 9.843 11.116 12.470 12.947WHSV (g/h/g) 27.74 19.36 15.37 12.19 10.79 9.62 9.27 Liquid yield (incl.H2O) 73.49 67.17 66.36 60.77 59.56 59.33 60.43 (wt %) IBP/221° C. perSim Dist 46.0370 50.7273 54.7000 57.2333 57.0741 59.8649 59.5294 (wt %)IBP/343° C. per Sim Dist 77.1481 81.2593 83.5676 86.0769 85.7838 87.516186.5676 (wt %) Normalized Mass Balance (wt. % of feed) H2 0.09 0.13 0.)50.18 0.19 0.26 0.22 H2S 0.00 0.00 0.00 0.00 0.00 0.00 0.00 CO 0.00 0.000.00 0.00 0.00 0.00 0.00 CO2 0.30 0.24 0.29 0.42 0.47 0.43 0.45 C1 0.300.41 0.48 0.61 0.81 0.93 0.82 C2 0.23 0.31 0.34 0.41 0.51 0.56 0.49 C2=0.39 0.54 0.60 0.67 0.72 0.69 0.75 Total Dry Gas 1.31 1.64 1.87 2.292.69 2.86 2.73 C3 0.65 0.74 0.82 1.01 1.51 1.79 1.55 C3= 2.62 3.32 3.553.81 3.78 3.85 3.92 i-C4 2.91 3.77 3.94 4.41 4.29 4.70 4.75 n-C4 0.640.84 0.87 1.02 1.07 1.18 1.13 i-C4= 0.76 0.94 0.96 1.03 1.01 1.00 1.02n-C4= 2.57 3.25 3.21 3.36 3.35 3.38 3.30 Total LPG 10.15 12.86 13.3614.64 15.01 15.89 15.67 Gasoline (C5-221° C.) 44.56 47.24 49.21 50.1449.42 49.71 49.30 LCO (221°-343° C.) 23.20 20.67 19.13 17.30 16.83 16.1516.14 HCO (343° C.+) 17.40 13.10 11.47 9.55 9.22 8.39 9.06 Coke 3.043.98 4.36 5.37 6.08 6.20 6.34 Total 99.7 99.5 99.4 99.3 99.3 99.2 99.2

TABLE 8 Run Number E-1 E-2 E-3 E-4 E-5 E-6 E-7 Dry Gas (lbs/hr) 1355.61867.8 2109.3 2511.4 2980.3 3265.7 3043.6 C3 (bbls/hr) 4.9 5.6 6.2 7.611.4 13.5 11.7 C3 = (bbls/hr) 19.2 24.3 26.0 27.9 27.7 28.2 28.8 C4(bbls/hr) 23.8 30.9 32.3 36.4 36.0 39.4 39.5 C4 = (bbls/hr) 21.1 26.526.3 27.8 27.6 27.7 27.3 C5-429 F Cut (bbls/hr) 217.8 228.3 240.4 239.9236.0 235.7 236.0 429-650 F Cut (bbls/hr) 92.6 82.5 76.3 69.0 67.1 64.464.4 650 F Cut (bbls/hr) 60.9 45.9 40.2 33.4 32.3 29.4 31.7 Coke((bs/hr) 4072.9 5337.2 5841.3 7192.0 8144.4 8315.0 8494.0 CO (lbs/hr) 00.0 0.0 0.0 0.0 0.0 0.0 CO2 (lbs/hr) 399.3 325.0 392.4 560.5 630.3 571.2608.5 H2O (lbs/hr) 2273.7 2493.5 2611.4 2756.1 2808.5 2867.5 2841.7 DryGas + CO + CO2 (lbs/hr) 1754.9 2192.8 2501.7 3071.9 3610.6 3837.0 3652.1Value/Cost 1.023 1.043 1.059 1.045 1.031 1.028 1.029 Water in Feed1798.8 1798.8 1798.8 1798.8 1798.8 1798.8 1798.8 Oxygen in Feed Water1599.0 1599.0 1599.0 1599.0 1599.0 1599.0 1599.0 Oxygen in Feed 27052705 2705 2705 2705 2705 2705 Oxygen in Total Prod. Water 2021.1 2216.52321.2 2449.8 2496.5 2548.9 2525.9 Oxygen % in water 74.7% 81.9% 85.8%90.6% 92.3% 94.2% 93.4% FCC Produced Water 474.9 694.7 812.5 957.21009.7 1068.7 1042.8 Delta CO2 produced from RFO 201.3 118.9 17.2 159.3193.6 42.7 80.0 Oxygen in Produced Water 422.1 617.5 722.3 850.9 897.5950.0 927.0 Oxygen in Delta CO2 146.4 86.5 12.5 115.8 140.8 31.1 58.2Oxygen in TLP (.26 DL) 312.5 312.5 312.5 312.5 312.5 312.5 312.5 TOTALOxygen 881.0 1016.5 1047.3 1279.2 1350.8 1293.5 1297.7 Delta Oxygen−225.1 −89.6 −58.8 173.1 244.7 187.4 191.6 Oxygen Balance (%) 91.6896.69 97.83 106.40 109.05 106.93 107.08 Amount of CO to Balance O2 393.9156.8 102.9 −303.0 −428.2 −328.0 Amount of H2O to Balance O2 253.2 100.866.1 −194.8 −275.3 −210.9 −215.5 Total H2O 2526.9 2594.3 2677.5 2561.32533.2 2656.7 2626.2

TABLE 9 Calculation of Gallons of Gasoline Attributed to the input ofRFO (on a 10,000 bbl/day input basis) Canmet MAT test Catalyst/Oil Ratio4 5 6 7 8 9 10 (approximated from curve-fitted line) Gasoline Makebbls/hr 208.53 217.58 225.27 231.63 236.63 240.29 242.60 (Ref. GO)10,000 bbls/day basis 134245 lbs/hr Gasoline Make bbls/ton 3.11 3.243.36 3.45 3.53 3.58 3.61 (Ref. GO) Gasoline Make bbls/hr 215.22 222.79228.98 233.80 237.26 239.35 240.07 (5 wt % RFO) 10,000 bbls/day  9,612bbls/day Ref. GO and 388 bbls/day RFO Gasoline Make bbls/hr 200.44209.14 216.53 222.64 227.45 230.96 233.19 attributed to Ref. GO(bbls/hr) vol. basis Gasoline Make bbls/hr 14.78 13.65 12.45 11.17 9.818.39 6.88 attributed to RFO by difference Gasoline Make bbls/ton 4.354.02 3.67 3.29 2.89 2.47 2.03 5 wt % RFO RFO Gasoline Make gals/ton of182.9 168.9 154.0 138.2 121.4 103.8 85.2 5 wt % RFO RFO (gals/ton ofRFO) Gasoline Make gals/ton of 128.0 118.2 107.8 96.7 85.0 72.6 59.6 5wt % RFO biomass assume 70 wt % yield

In the description above, for purposes of explanation only, specificembodiments have been presented and/or exemplified. It should beunderstood that variations of various aspects of an embodiment may becombined with other stated components, embodiments, ranges, types, etc.For example, there are embodiments that discuss the processing of an RFOand it should be understood that any and all of the types of RFO'sdiscussed and/or presented herein may be substituted and/or combinedinto such embodiments even though an embodiment may not be specificallypresented with the particular type of RFO in the description.

While numerous embodiments of the present invention have been shown anddescribed herein, it will be obvious to those skilled in the art thatsuch embodiments are provided by way of example only. It is intendedthat the following claims or future claims that may be added and/oramended in this or future continuing applications, in this or othercountries and territories, define the scope of the invention and thatmethods and structures and products and uses within the scope of theseclaims and their equivalents be covered thereby.

What is claimed is:
 1. A method to reduce the generation of wastestreams when preparing a fuel, comprising: converting a cellulosicbiomass into an unenriched renewable fuel oil by mechanical and thermalprocessing, comprising: i) grinding the cellulosic biomass to form aground cellulosic biomass, and ii) non-catalytic rapid thermalprocessing of the ground cellulosic biomass to convert at least 60 wt. %of the ground cellulosic biomass to the unenriched renewable fuel oil;devolatilizing the unenriched renewable fuel oil to produce anunenriched reduced-volatility renewable fuel oil, the unenrichedreduced-volatility renewable fuel oil having a flash point in the rangeof 55-62 degrees C. as measured by the Pensky-Martens closed cup flashpoint tester; and processing a feedstock in a fluidized catalyticcracker, the feedstock comprising: i) 93-99.95 wt. % of a petroleumfraction, and ii) 0.05-7 wt. % of the unenriched reduced-volatilityrenewable fuel oil.
 2. The method of claim 1, wherein the devolatizingcomprises processing the unenriched renewable fuel oil in a wiped-filmevaporator.
 3. The method of claim 1, wherein the devolatizing comprisesprocessing the unenriched renewable fuel oil in a falling filmevaporator.
 4. The method of claim 1, wherein the devolatizing comprisesprocessing the unenriched renewable fuel oil in a flash column.
 5. Themethod of claim 1, wherein the devolatizing comprises processing theunenriched renewable fuel oil in a packed column.
 6. The method of claim1, wherein the devolatizing comprises processing the unenrichedrenewable fuel oil in a devolatilization vessel.
 7. The method of claim1, wherein the unenriched reduced-volatility renewable fuel oil has areduced weight percentage of phenols relative to the unenrichedrenewable fuel oil.
 8. The method of claim 7, wherein the unenrichedrenewable fuel oil has a solids content of less than 0.5 wt. % and anash content of less than 0.1 wt. %.
 9. The method of claim 8, whereinthe cellulosic biomass comprises wood, wood residues, or sawdust. 10.The method of claim 9, wherein the cellulosic biomass comprises woodresidues.
 11. The method of claim 8, wherein the cellulosic biomasscomprises bagasse, palm fronds, or empty fruit bunches.
 12. The methodof claim 1, wherein the unenriched renewable fuel oil has a solidscontent of less than 0.1 wt. %.
 13. The method of claim 1, wherein thecellulosic biomass comprises wood, wood residues, or sawdust.
 14. Themethod of claim 13, wherein the cellulosic biomass comprises woodresidues.
 15. The method of claim 14, wherein the unenriched renewablefuel oil has a solids content of less than 0.5 wt. % and an ash contentof less than 0.1 wt. %.
 16. The method of claim 1, wherein thecellulosic biomass comprises bagasse, palm fronds, or empty fruitbunches.
 17. The method of claim 1, wherein the unenriched renewablefuel oil has an ash content of less than 0.05 wt. %.